U.S. patent application number 15/617970 was filed with the patent office on 2017-11-23 for methods of synthesizing an oxidant and applications thereof.
The applicant listed for this patent is Ferrate Treatment Technologies, LLC. Invention is credited to Lee Edward Ciampi, Luke J. Daly.
Application Number | 20170334753 15/617970 |
Document ID | / |
Family ID | 36579473 |
Filed Date | 2017-11-23 |
United States Patent
Application |
20170334753 |
Kind Code |
A1 |
Ciampi; Lee Edward ; et
al. |
November 23, 2017 |
METHODS OF SYNTHESIZING AN OXIDANT AND APPLICATIONS THEREOF
Abstract
Novel devices for synthesizing ferrate and uses thereof are
described. One aspect of the invention relates to devices and
systems for synthesizing ferrate at a site proximal to the site of
use.
Inventors: |
Ciampi; Lee Edward; (St.
Paul, MN) ; Daly; Luke J.; (Belle Isle, FL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Ferrate Treatment Technologies, LLC |
Orlando |
FL |
US |
|
|
Family ID: |
36579473 |
Appl. No.: |
15/617970 |
Filed: |
June 8, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14866426 |
Sep 25, 2015 |
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15617970 |
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14052590 |
Oct 11, 2013 |
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14866426 |
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13615391 |
Sep 13, 2012 |
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14052590 |
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13419363 |
Mar 13, 2012 |
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13615391 |
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12911652 |
Oct 25, 2010 |
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13419363 |
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12352405 |
Jan 12, 2009 |
7820025 |
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12911652 |
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10997333 |
Nov 24, 2004 |
7476324 |
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12352405 |
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10824268 |
Apr 14, 2004 |
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10997333 |
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10246575 |
Sep 17, 2002 |
6974562 |
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10824268 |
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10047460 |
Jan 14, 2002 |
6790429 |
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10246575 |
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09905165 |
Jul 12, 2001 |
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10047460 |
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60218409 |
Jul 14, 2000 |
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60299884 |
Jun 21, 2001 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C02F 1/5236 20130101;
C01G 49/0081 20130101; C25B 1/00 20130101; C02F 2103/008 20130101;
C02F 2303/04 20130101; C02F 1/72 20130101 |
International
Class: |
C02F 1/52 20060101
C02F001/52; C01G 49/00 20060101 C01G049/00; C02F 1/72 20060101
C02F001/72; C25B 1/00 20060101 C25B001/00 |
Claims
1. A method of treating, at a site of use, an aqueous mixture
having at least one impurity, comprising a) continuously generating
ferrate at a location that is proximal to the site of use; b)
contacting the ferrate with the aqueous mixture at the site of use,
whereby at least a portion of the impurity is oxidized or
coagulated.
2. The method of claim 1, wherein the step of continuously
generating ferrate comprises the steps of: a) mixing an aqueous
solution comprising an iron salt and an oxidizing agent in a mixing
chamber; b) delivering at least a portion of the aqueous solution
to a reaction chamber; c) continuously generating ferrate in the
reaction chamber; d) delivering at least a portion of the ferrate
to a site of use that is proximal to the reaction chamber; and e)
adding additional aqueous solution to the mixing chamber.
3. The method of claim 2, further comprising the step of adding a
base to the aqueous solution.
4. The method of claim 1, whereby at least a portion of the
impurity is coagulated.
5. The method of claim 1, wherein the aqueous mixture is drinking
water.
6. The method of claim 1, wherein the aqueous mixture is waste
water.
7. The method of claim 1, wherein the aqueous mixture is sewage
water.
8. The method of claim 1, wherein the step of continuously
generating ferrate is performed in a reaction chamber.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of U.S. patent
application Ser. No. 14/866,426, entitled "METHODS OF SYNTHESIZING
AN OXIDANT AND APPLICATIONS THEREOF" now pending, which in turn is
a continuation of U.S. patent application Ser. No. 14/052,590,
entitled "METHODS OF SYNTHESIZING AN OXIDANT AND APPLICATIONS
THEREOF" now abandoned, which in turn is a continuation of U.S.
patent application Ser. No. 13/615,391, entitled "METHODS OF
SYNTHESIZING AN OXIDANT AND APPLICATIONS THEREOF" now abandoned,
which in turn is a continuation of U.S. patent application Ser. No.
13/419,363, entitled "METHODS OF SYNTHESIZING AN OXIDANT AND
APPLICATIONS THEREOF" now abandoned, which in turn is a
continuation of Ser. No. 12/911,652, filed Oct. 25, 2010, entitled
"METHODS OF SYNTHESIZING AN OXIDANT AND APPLICATIONS THEREOF," now
abandoned, which in turn is a continuation of U.S. patent
application Ser. No. 12/352,405, filed Jan. 12, 2009, entitled
"METHODS OF SYNTHESIZING AN OXIDANT AND APPLICATIONS THEREOF,"
which is now U.S. Pat. No. 7,820,025, which in turn is a
continuation of U.S. patent application Ser. No. 10/997,333, filed
Nov. 24, 2004, entitled "METHODS OF SYNTHESIZING AN OXIDANT AND
APPLICATIONS THEREOF," which is now U.S. Pat. No. 7,476,324, which
in turn is a continuation of U.S. patent application Ser. No.
10/824,268, filed Apr. 14, 2004, now abandoned, which in turn is a
continuation-in-part of U.S. patent application Ser. No.
10/246,575, filed Sep. 17, 2002, entitled "METHODS OF SYNTHESIZING
AN OXIDANT AND APPLICATIONS THEREOF," which is now U.S. Pat. No.
6,974,562, which in turn is a continuation of U.S. patent
application Ser. No. 10/047,460, filed Jan. 14, 2002, entitled
"METHODS OF SYNTHESIZING AN OXIDANT AND APPLICATIONS THEREOF,"
which is now U.S. Pat. No. 6,790,429, which in turn is a
continuation-in-part of the U.S. patent application Ser. No.
09/905,165, filed Jul. 12, 2001, now abandoned, which in turn
claims priority to U.S. Provisional Patent Application No.
60/218,409, filed Jul. 14, 2000, and U.S. Provisional Patent
Application No. 60/299,884, filed Jun. 21, 2001, all of which are
incorporated by reference herein in their entirety, including any
drawings.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The present invention relates, generally, to the manufacture
and the application of the ferrate ion. More particularly, the
present invention relates to methods and systems for treating, with
the ferrate ion, solutions containing impurities.
Description of the Related Art
[0003] The ferrate ion, FeO.sub.4.sup.2-, is a tetrahedral ion that
is believed to be isostructural with chromate, CrO.sub.4.sup.2-,
and permanganate, MnO.sub.4.sup.-. The ferrate ion has been
suggested to exist in aqueous media as the tetrahedral species
FeO.sub.4.sup.2-. Redox potentials for FeO.sub.4.sup.2- ion have
been estimated in both acidic and basic media (R. H. Wood, J. Am.
Chem. Soc., Vol. 80, p. 2038-2041 (1957)):
FeO.sub.4.sup.2-+8H.sup.++3e.sup.-.fwdarw.Fe.sup.3++4H.sub.2O
E.degree.=2.20V
FeO.sub.4.sup.2-+4H.sub.2O+3e.sup.-.fwdarw.Fe.sup.3++8OH.sup.-
E.degree.=0.72V
[0004] Ferrate is a strong oxidant that can react with a variety of
inorganic or organic reducing agents and substrates (R. L.
Bartzatt, J. Carr, Trans. Met. Chem., Vol. 11 (11), pp. 414-416
(1986); T. J. Audette, J. Quail, and P. Smith, J. Tetr. Lett., Vol.
2, pp. 279-282 (1971); D. Darling, V. Kumari, and J. BeMiller, J.
Tetr. Lett., Vol. 40, p. 4143 (1972); and R. K. Murmann and H. J.
Goff, J. Am. Chem. Soc., Vol. 93, p. 6058-6065 (1971)). It can,
therefore, act as a selective oxidant for synthetic organic studies
and is capable of oxidizing/removing a variety of organic and
inorganic compounds from, and of destroying many contaminants in,
aqueous and non-aqueous media.
[0005] In the absence of a more suitable reductant, ferrate will
react with water to form ferric ion and molecular oxygen according
to the following equation (J. Gump, W. Wagner, and E. Hart, Anal.
Chem., Vol. 24., p. 1497-1498 (1952)).
4FeO.sub.4.sup.2-+10H.sub.2O.fwdarw.Fe.sup.3++20OH.sup.-+3O.sub.2
[0006] This reaction is of particular interest to water treatment
because it provides a suitable mechanism for self-removal of
ferrate from solution. In all oxidation reactions, the final iron
product is the non-toxic ferric ion which forms hydroxide
oligomers. Eventually flocculation and settling occur which remove
suspended particulate matter.
[0007] The use of ferrate may therefore provide a safe, convenient,
versatile and cost effective alternative to current approaches for
water, wastewater, and sludge treatment. In this regard, ferrate is
an environmentally friendly oxidant that represents a viable
substitute for other oxidants, particularly chromate and chlorine,
which are of environmental concern. Ferric oxide, typically known
as rust, is the iron product of oxidation by ferrate. Therefore,
ferrate has the distinction of being an "environmentally safe"
oxidant. Although the oxidation reactions with ferrate appear
similar to those known for MnO.sub.4.sup.- and CrO.sub.4.sup.2-,
ferrate exhibits greater functional group selectivity with higher
rate of reactivity in its oxidations and generally reacts to
produce a cleaner reaction product.
[0008] One problem hindering ferrate implementation is difficulty
in its preparation. This difficulty may lead to increased
production costs. Moreover, in addition to cost, the current
methods known for producing a commercially useful and effective
ferrate product, and the results of these methods, have been less
than satisfactory. There exists a need for new synthetic
preparative procedures that are easier and less expensive in order
to provide ferrate material at economically competitive prices.
[0009] Three approaches for ferrate synthesis are known:
electrolysis, oxidation of Fe.sub.2O.sub.3 in an alkaline melt, or
oxidation of Fe(III) in a concentrated alkaline solution with a
strong oxidant.
[0010] In the laboratory, by means of hypochlorite oxidation of
iron (Fe(III)) in strongly alkaline (NaOH) solution, the ferrate
product has been precipitated by the addition of saturated KOH (G.
Thompson, L. Ockerman, and J. Schreyer, J. Am. Chem. Soc., Vol. 73,
pp. 1379-81 (1951)):
2Fe.sup.3++3OCl.sup.-+10OH.sup.-.fwdarw.FeO.sub.4.sup.2-+3Cl.sup.-+5H.su-
b.2O
The resulting purple solid is stable indefinitely when kept
dry.
[0011] Commercial production of ferrate typically uses a synthetic
scheme similar to the laboratory preparation, also involving a
hypochlorite reaction. Most commonly, using alkaline oxidation of
Fe(III), potassium ferrate (K.sub.2FeO.sub.4) is prepared via
gaseous chlorine oxidation in caustic soda of ferric hydroxide,
involving a hypochlorite intermediate. Another method for ferrate
production was described by Johnson in U.S. Pat. No. 5,746,994.
[0012] A number of difficulties are associated with the production
of ferrate using the method described above. For example, several
requirements for reagent purity must be ensured for maximized
ferrate yield and purity. However, even with these requirements
satisfied, the purity of the potassium ferrate product still varies
widely and depends upon many factors, such as reaction time,
temperature, purity of reagents, and isolation process. Ferrate
prepared this way generally contains impurities, with the major
contaminants being alkali metal hydroxides and chlorides and ferric
oxide. However, samples of this degree of purity are unstable and
readily decompose completely into ferric oxides.
[0013] Other than the specific problems with product impurities and
instability, there also exist mechanical problems associated with
the isolation of the solid ferrate product, such as filtering cold
lye solutions having a syrupy consistency.
[0014] Other processes for preparation of ferrates are known and
used, many of them also involving the reactions with hypochlorite.
For example, U.S. Pat. No. 5,202,108 to Deininger discloses a
process for making stable, high-purity ferrate (VI) using
beta-ferric oxide (beta-Fe.sub.2O.sub.3) and preferably
monohydrated beta-ferric oxide (beta-Fe.sub.2O.sub.3.H.sub.2O),
where the unused product stream can be recycled to the ferrate
reactor for production of additional ferrate.
[0015] U.S. Pat. Nos. 4,385,045 and 4,551,326 to Thompson disclose
a method for direct preparation of an alkali metal or alkaline
earth metal ferrates from inexpensive, readily available starting
materials, where the iron in the product has a valence of +4 or +6.
The method involves reacting iron oxide with an alkali metal oxide
or peroxide in an oxygen free atmosphere or by reacting elemental
iron with an alkali metal peroxide in an oxygen free
atmosphere.
[0016] U.S. Pat. No. 4,405,573 to Deininger et al. discloses a
process for making potassium ferrate in large-scale quantities
(designed to be a commercial process) by reacting potassium
hydroxide, chlorine, and a ferric salt in the presence of a ferrate
stabilizing compound.
[0017] U.S. Pat. No. 4,500,499 to Kaczur et al. discloses a method
for obtaining highly purified alkali metal or alkaline earth metal
ferrate salts from a crude ferrate reaction mixture, using both
batch and continuous modes of operation.
[0018] U.S. Pat. No. 4,304,760 to Mein et al. discloses a method
for selectively removing potassium hydroxide from crystallized
potassium ferrate by washing it with an aqueous solution of a
potassium salt (preferably a phosphate salt to promote the
stability of the ferrate in the solid phase as well as in aqueous
solution) and an inorganic acid at an alkaline pH.
[0019] U.S. Pat. No. 2,758,090 to Mills et al. discloses a method
of making ferrate, involving a reaction with hypochlorite, as well
as a method of stabilizing the ferrate product so that it can be
used as an oxidizing agent.
[0020] U.S. Pat. No. 2,835,553 to Harrison et al. discloses a
method, using a heating step, where novel alkali metal ferrates
with a valence of +4 are prepared by reacting the ferrate (III) of
an alkali metal with the oxide (or peroxide) of the same, or a
different, alkali metal to yield the corresponding ferrate
(IV).
[0021] U.S. Pat. No. 5,284,642 to Evrard et al. discloses the
preparation of alkali or alkaline earth metal ferrates that are
stable and industrially usable as oxidizers, and the use of these
ferrates for water treatment by oxidation. Sulfate stabilization is
also disclosed.
[0022] The development of an economical source of ferrate is
desired to derive the benefits associated with ferrate application
in a wide range of processes. In view of the difficulties
associated with the previously known methods for preparing ferrates
and the problems inherent in the ferrate produced by these known
methods, there is therefore an existing need for a new preparative
method for ferrate that is easy, convenient, safe and inexpensive,
and that avoids both the chemical and mechanical problems. There
also exists a need for a system which reduces or counteracts the
limited stability of ferrate, and systems which employ ferrate as
an environmentally friendly oxidant and disinfectant.
SUMMARY OF THE INVENTION
[0023] A method of continuously synthesizing ferrate is disclosed,
comprising mixing a mixture comprising an iron salt and an
oxidizing agent in a mixing chamber; delivering at least a portion
of the mixture to a reaction chamber; continuously generating
ferrate in the reaction chamber; delivering at least a portion of
the ferrate to a site of use that is proximal to the reaction
chamber; and adding additional iron salt and oxidizing agent to the
mixing chamber.
[0024] Also disclosed is a method of treating, at a site of use, a
mixture having at least one impurity, comprising continuously
generating ferrate in a reaction chamber located proximal to the
site of use; contacting the ferrate with the mixture at the site of
use, whereby at least a portion of the impurity is oxidized.
[0025] Also disclosed is a device for continuously synthesizing
ferrate, comprising a first holding chamber; a second holding
chamber; a mixing chamber controllably connected to the first
holding chamber and to the second holding chamber, into which a
content of the first holding chamber and a content of a second
holding chamber are added to form a mixture; a reaction chamber
controllably connected to the mixing chamber, into which the
mixture is kept for a period of time; and an output opening in the
reaction chamber through which the mixture may be transported to a
proximal site of use.
[0026] Also disclosed is a system for continuously synthesizing
ferrate, comprising a first holding chamber containing an iron
salt; a second holding chamber containing an oxidizing agent; a
mixing chamber controllably connected to the first holding chamber
and to the second holding chamber, into which the iron salt and the
oxidizing agent are controllably added to form a mixture; a
reaction chamber controllably connected to the mixing chamber, into
which the mixture is kept for a period of time, and in which
ferrate is synthesized, and an output opening in the reaction
chamber through which the ferrate may be transported to a proximal
site of use. The "period of time" during which the mixture is kept
in the reaction chamber may range from seconds to hours to days,
but may be any time longer than zero seconds.
[0027] Also disclosed is a method of continuously synthesizing
ferrate, comprising providing a mixture of an iron salt and an
oxidizing agent; continuously delivering at least a portion of the
mixture to a heating chamber; exposing the mixture to elevated
temperatures in the heating chamber, thereby generating ferrate;
removing at least a portion of the generated ferrate from the
heating chamber; adding additional mixture to the heating
chamber.
[0028] Also disclosed is a device for continuously synthesizing
ferrate, comprising a holding chamber; a mover controllably
connected to the holding chamber such that at least a portion of a
content of the holding chamber is transferred to the mover; a
heating chamber, through which at least a portion of the mover
moves; an output opening in the heating chamber through which the
content on the mover may be transported to a proximal site of
use.
[0029] Also disclosed is a device for continuously synthesizing
ferrate, comprising a mixing chamber comprising two electrodes,
where the electrodes provide sufficient electric current to convert
a solution of an iron salt to a solution of ferrate; a reaction
chamber controllably connected to the mixing chamber, into which
the mixture is kept for a period of time; and an output opening in
the reaction chamber through which the mixture may be transported
to a proximal site of use. The mixture is kept in the reaction
chamber for a period of time longer than zero seconds.
[0030] Also disclosed is a method of continuously synthesizing
ferrate, comprising continuously providing an aqueous solution
comprising an iron salt in a mixing chamber, where the mixing
chamber comprises at least two electrodes; providing sufficient
electric current to the at least two electrodes to convert at least
a portion of the iron salt to ferrate; delivering at least a
portion of the ferrate to a site of use that is proximal to the
reaction chamber; and adding additional aqueous solution to the
mixing chamber.
[0031] Also disclosed is a method of synthesizing ferrate,
comprising mixing a mixture comprising an iron salt and an
oxidizing agent in a mixing chamber; delivering at least a portion
of the ferrate to a site of use that is proximal to the mixing
chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] FIGS. 1A-B depict embodiments of devices for solution phase
synthesis of ferrate ion.
[0033] FIG. 2 depicts an embodiment of the device for solid phase
synthesis of ferrate ion.
[0034] FIG. 3 depicts an embodiment of the device for
electrochemical synthesis of ferrate ion.
[0035] FIG. 4 is a flow chart depicting some embodiments of the
process of generating and purifying ferrate.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0036] It is an object of the invention to provide a new,
convenient, inexpensive, and safe method for producing a salt of
ferrate. Such a method may produce the sodium salt, but may be used
to prepare other salts of Group I or Group II cations, or other
cations, whether metallic or not.
[0037] It is an object of the invention to provide an
environmentally friendly oxidant for application in a variety of
wastewater contaminants and water treatment problems. Such an
oxidant produces a cleaner reaction product(s) and thereby may be
used to replace existing environmental, laboratory, and industrial
oxidants which may have deleterious side effects or costs.
[0038] It is an object of the invention to provide a new, safe, and
inexpensive industrial and environmental remediation chemical
oxidant that overcomes the problems associated with known oxidants
for water treatment (for example, chlorine, hypochlorite, chlorine
dioxide, permanganate, and ozone) and the by-products of these
oxidants.
[0039] It is an object of this invention to provide a new ferrate
product to be used in the control of sulfides, including hydrogen
sulfide gas, in sewer systems, ground water, treatment plants, and
waste treatment facilities.
[0040] It is an object of the invention to provide an improved
ferrate product for remediation of uranium, transuranics, rocket
fuel propellant contaminants (hydrazine and monomethylhydrazines)
and mustard gas.
[0041] It is a further object of the invention to provide an
innovative product to be used as coagulant and disinfectant.
[0042] It is an object of the present invention to provide an
oxidant to be used in drinking water disinfection and coagulation,
biofouling control, ground water decontamination, solid surface
washing, and hazardous waste treatment.
[0043] It is an object of the present invention to provide an
oxidant to be used in synthetic chemistry.
[0044] It is an object of the present invention to provide an
oxidant to be used in surface preparation, including polymer
surface and metallic surface preparation.
[0045] To achieve at least one of the above-stated objectives, the
following methods, manufactures, compositions of matter, and uses
thereof are provided.
I. ON-SITE GENERATION
[0046] The inventors have discovered that many of the presently
unaddressed problems associated with ferrate use relate to the
purification and storage of ferrate. Therefore, in some embodiments
of the invention, a system of producing ferrate and using it
without substantially further purification, packaging, or
preparation is provided. Because ferrate, in its unpurified form
decomposes rather rapidly, the ferrate produced by the provided
methods need not be stored. Ferrate may, and preferably is, used
immediately, or substantially soon after its generation. Therefore,
certain embodiments of the present invention provide a device that
is designed to be located in close proximity to the site of use,
such that when ferrate is produced, it may be rapidly and
efficiently delivered to the site of use, without substantial
further purification, packaging, shipping, transfer, or
preparation.
[0047] As used herein, the terms "site of generation" or
"generation site" refer to the site where the device for the
generation of ferrate is located. In one embodiment exemplified
herein, the generation site includes a reaction chamber for
generation of ferrate. The terms "site of use," "use site," or
"treatment site" refer to the site where the ferrate is contacted
with the object it is to oxidize, synthesize, disinfect, clean,
plate, encapsulate, or coagulate.
[0048] The terms "close proximity" and "proximal" are used
interchangeably herein. These terms are used to refer to the
relative locations of the generation site and the use site when the
two sites are within a distance that allows for the ferrate to
travel the distance within a half-life of its decomposition.
"Half-life" of a decomposition is understood to be the amount of
time it takes for one half of the material present to undergo
decomposition. The half-life for any given ferrate composition will
depend on the conditions under which the ferrate is generated
and/or stored. Thus, for example, the temperature, concentration of
base, concentration of oxidizing agent and presence of impurities
will all tend to affect the half-life of the ferrate composition.
However, the half-life can be readily measured by those having
ordinary skill in the art using conventional techniques. Therefore,
a generation site is "proximal" to a use site when the
concentration of ferrate at the use site at the time of delivery is
equal to or greater than one-half of the concentration of ferrate
at the generation site. The distance between the generation site
and the use site is defined in terms of the half-life and a length
of time required for delivery, rather than simply in terms of
physical displacement. Thus, the physical displacement between a
generation site and use site that are in close proximity may vary
depending on the half-life of the ferrate composition being
delivered between the two sites and the rate at which the
composition is delivered. Accordingly factors affecting both the
rate of ferrate transfer and factors affecting the half-life will
all affect the maximum physical displacement permissible for the
two sites to remain in close proximity. Factors affecting the rate
of ferrate transfer include, but are not limited to, the pressure
generated by a pump used in the transfer and the size of the
plumbing used in the transfer.
[0049] The on-site generation methods provide a number of
advantages over known processes. Initially, because the produced
ferrate can be used without further substantial purification or
stabilization, there is no need for storage or shipping. In
addition, eliminating the need for a highly purified ferrate
ultimately saves costs by increasing the yield of the reaction
because less starting materials are needed to afford the same
amount of usable ferrate.
[0050] The current practice for making and purifying ferrate
involves the production of sodium ferrate using sodium hydroxide,
followed by the precipitation of potassium ferrate using potassium
hydroxide. Thus, the current methods use base in two distinct
steps. The methods of some of the embodiments of the present
invention require substantially less base to produce usable ferrate
since the methods do not require the addition of potassium
hydroxide to sodium ferrate.
[0051] Thus, the ferrate produced by some of the methods of the
present invention can be used or purified in a solution-to-solution
phase manner, i.e., ferrate is generated in the solution phase and
is used in the solution phase, without the intervening
crystallization, or conversion to the solid phase (i.e.,
solution-to-solid phase). If partial purification or separation is
required, then such purification or separation can be achieved in
the solution phase as well. In certain embodiments of the present
invention, the produced ferrate is not converted to any phase other
than the solution phase.
[0052] The solution-to-solution phase concept discussed above
provides advantages over the solution-to-solid phase method. For
example, as discussed above, conversion to solid or crystallization
is limited by the nature of the counter-ion. Crystallization of
potassium ferrate is less difficult than crystallization of sodium
ferrate. Ferrate with certain counter-ions can never be
crystallized or can be crystallized under very difficult
conditions. Using the solution-to-solution phase concept, virtually
any counter-ion can be used. In addition, once ferrate is
crystallized, it would have to be re-dissolved in aqueous media for
use. The re-dissolution of ferrate adds both cost (loss of ferrate,
addition of water, and dissolution tanks, to name a few) and time
(dissolution time) to the process. In the solution-to-solution
phase method, ferrate is already in aqueous solution and can be
used as such. Furthermore, if pH is to be adjusted, it is more
efficient to adjust the pH of the ferrate stream once it is
produced than to adjust the pH of a ferrate solution prepared from
adding solid ferrate to water. Yet another advantage of the
solution-to-solution phase concept is the ease of production of
custom blends.
[0053] The above advantages result in the entire process being
cheaper and more economical than the available processes. The
relatively low cost of production allows the ferrate to be used in
a large variety of settings, which heretofore have been
substantially unavailable for the oxidizing benefits of the
compound due to its cost. Most importantly, ferrate may now be made
available to municipal water and wastewater treatment facilities,
which are cost conscious.
[0054] Furthermore, on-site generation of ferrate allows the end
user to control the amount of ferrate to be produced. This may
alleviate or reduce the need for inventory control of ferrate, in
addition to alleviating or reducing the need to store ferrate.
II. PROCESS FOR PREPARING FERRATE
A. Solution Phase Production
[0055] In one aspect, the invention relates to a method of
continuously synthesizing ferrate, comprising mixing an iron salt
and an oxidizing agent in a mixing chamber to form a mixture;
delivering at least a portion of the mixture to a reaction chamber;
continuously generating ferrate in the reaction chamber; delivering
at least a portion of the ferrate to a site of use that is proximal
to the reaction chamber; and adding additional iron salt and
oxidizing agent to the mixing chamber.
[0056] In certain embodiments, the above method further comprises
the addition of a solvent during the mixing step. In some
embodiments, the solvent is water and the mixture is, therefore, an
aqueous solution. In other embodiments, the mixture is a
non-aqueous solution. In certain other embodiments, the oxidizing
agent may be a neat liquid, in which case it would act as a solvent
for dissolving the iron salt as well. In still other embodiments,
the iron salt and the oxidizing agent are added as solids, and the
reaction takes place in solid form.
[0057] Thus, one embodiment of the invention relates to a method of
continuously synthesizing ferrate, comprising mixing an aqueous
solution comprising an iron salt and an oxidizing agent in a mixing
chamber; delivering at least a portion of the aqueous solution to a
reaction chamber; continuously generating ferrate in the reaction
chamber; delivering at least a portion of the ferrate to a site of
use that is proximal to the reaction chamber; and adding additional
aqueous solution to the mixing chamber.
[0058] It is known to those of skill in the art that iron can
accommodate an oxidation state in the range of 0 to +8, including
the +1, +2, +3, +4, +5, +6, and +7 oxidation states. Iron in the 0
oxidation state is elemental iron. Most compounds and salts of iron
found in nature have an oxidation state of either +2 (Fe(II)) or +3
(Fe(III)). In the context of the present invention, "ferrate"
refers to an ion comprising iron in its +4, +5, +6, +7, or +8
oxidation states, i.e., comprising Fe(IV), Fe(V), Fe(VI), Fe(VII),
or Fe(VIII). The ferrate ion also contains oxygen atoms. It may or
may not comprise atoms of other elements. Furthermore, "ferrate"
may also refer to a mixture of ions comprising iron in various
oxidation states, as long as at least a portion of the ions
comprise iron exhibiting an oxidation state of +4 or higher. Thus,
for example, ferrate refers to a FeO.sub.4.sup.2-, where the iron
is Fe(VI) and the other atoms in the ion are oxygen atoms. A
solution comprising FeO.sub.4.sup.2- ions may also contain ions
exhibiting iron in its +5 oxidation state, or any other oxidation
state, including the elemental form of iron, and it would still be
called ferrate. Similarly, a ferrate solution may contain no Fe(VI)
containing ions. A ferrate solution may also comprise Fe(V) or
Fe(IV) containing ions. Therefore, any ion comprising Fe(IV), or
higher oxidation state iron atoms, and at least one oxygen atom is
considered to be "ferrate." Ferrate ions may be either cations or
anions.
[0059] It is understood by those skilled in the art that any ion
requires a counterion of equal, though opposite, charge. This is
also true for the ferrate ions of the present invention. The
counterion may be any ion that renders neutral the overall charge
of the mixture comprising the ferrate ion. When ferrate is an
anion, the counterion may be any cation. The most common form of
ferrate to-date is K.sub.2FeO.sub.4, where the iron is in its +6
oxidation state, the ferrate is an anion and the counterion is
potassium. Any other counter-cation, such as, and without
limitation, sodium, calcium, magnesium, silver, etc., may also be
present.
[0060] By "continuously generating" or "continuously synthesizing"
it is meant that once ferrate begins to be delivered to the
reaction chamber, there continues to be an amount of ferrate in the
reaction chamber for the duration of time that the method is being
practiced. Thus, as described hereinbelow in greater detail, in one
embodiment of a continuous generation process in accordance with
the present invention, there is a constant flow of material from
the mixing chamber to the reaction chamber. In other embodiments,
as also described hereinbelow, material is intermittantly
transferred from the mixing chamber to the reaction chamber while
maintaining at least some ferrate in the reaction chamber.
[0061] In certain embodiments, the additional mixture of iron salt
and oxidizing agent of the above method is added in an amount to
substantially replace the portion of the mixture delivered to the
reaction chamber. In the context of the present invention, for a
second amount to substantially replace a first amount, the second
amount may be less than, equal to, or greater than the first
amount.
[0062] In certain embodiments, the method of producing ferrate
further comprises adding a base to the mixture. The base may
comprise a nitrogen base or an ion selected from the group
consisting of hydroxide, oxide, sulfonate, sulfate, sulfite,
hydrosulfide, phosphate, acetate, bicarbonate, and carbonate, or a
combination thereof "Nitrogen bases" are selected from acyclic and
cyclic amines. Examples of nitrogen bases include, but are not
limited to, ammonia, amide, methylamine, methylamide,
trimethylamine, trimethylamide, triethylamine, triethylamide,
aniline, pyrrolidine, piperidine, and pyridine, or salts
thereof.
[0063] To produce ferrate by the methods of the present invention,
an iron salt must be provided. "Iron salt" or "salt of iron" refers
to a compound that comprises an iron atom in an oxidation state
other than zero. The iron salt used by the methods of the present
invention may be produced in situ, i.e., by oxidizing elemental
iron either chemically or electrochemically prior to its
introduction into the mixing chamber or by performing the oxidation
inside the mixing chamber. The iron atom in the iron salt will have
an oxidation state greater than zero, preferably +2 or +3, though
this oxidation state may be reached transiently as the iron atom is
converted from its starting oxidation state to the final oxidation
state of +4 or above.
[0064] In certain embodiments, the iron salt may be selected from
the group consisting of ferric nitrate, ferrous nitrate, ferric
chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric
sulfate, ferrous sulfate, ferric phosphate, ferrous phosphate,
ferric hydroxide, ferrous hydroxide, ferric oxides, ferrous oxides,
ferric hydrogen carbonate, ferrous hydrogen carbonate, ferric
carbonate, and ferrous carbonate, or a combination thereof. All
different forms of ferric and ferrous oxide are contemplated to be
used with the methods of the present invention.
[0065] In some embodiments of the present invention, ferrate is
produced by chemical oxidation of the iron salt. The chemical
oxidation is performed by mixing an oxidizing agent, or a solution
containing the oxidizing agent, with the iron salt, or with the
solution containing the iron salt. In some embodiments, the
oxidizing agent, or a solution containing the oxidizing agent, is
added to the iron salt, or to the solution containing the iron
salt, whereas in other embodiments, the iron salt, or the solution
containing the iron salt, is added to the oxidizing agent, or to a
solution containing the oxidizing agent. An "oxidizing agent" is a
chemical compound that oxidizes another compound, and itself is
reduced. In certain embodiments, the oxidizing agent comprises at
least one of the following: a hypohalite ion, a halite ion, a
halate ion, a perhalate ion, ozone, oxone, halogen, a peroxide, a
superoxide, a peracid, a salt of a peracid, and Caro's acid, or a
combination thereof.
[0066] Embodiments of the invention include those in which the
oxidizing agent comprises a hypohalite ion selected from the group
consisting of the hypochlorite ion, the hypobromite ion, and the
hypoiodite ion. In other embodiments of the invention, the
oxidizing agent comprises a halite ion selected from the group
consisting of the chlorite ion, the bromite ion, and the iodite
ion. In yet other embodiments of the invention, the oxidizing agent
comprises a halate ion selected from the group consisting of the
chlorate ion, the bromate ion, and the iodate ion. Certain other
embodiments of the invention include those in which the oxidizing
agent comprises a perhalate ion selected from the group consisting
of the perchlorate ion, the perbromate ion, and the periodate
ion.
[0067] Thus, in an embodiment of the present invention, an aqueous
solution of an iron salt and an oxidizing agent is mixed in a
mixing chamber. A base, or a combination of bases, may also be
added to the mixing chamber at this time. The solution is mixed in
the mixing chamber for a certain period of time, which may range
from seconds to hours depending on the conditions of the mixing,
e.g., the temperature or the concentration of the ingredients.
Those skilled in the art recognize that at this stage ferrate
production begins.
[0068] As the mixing is taking place, at least a portion of the
mixture is delivered to a reaction chamber. The mixture is held in
the reaction chamber for a certain period of time until the amount
of ferrate in the mixture, e.g., the concentration of ferrate in an
aqueous solution, reaches a pre-determined level. The concentration
of ferrate for use is determined based on the need for the ferrate
and the conditions for the synthesis or use. Certain applications
may require higher yields of ferrate than others. Therefore, the
time that mixture remains in the reaction chamber may range from
seconds to hours. The reaction chamber may also be used as a
"holding tank," i.e., a place to keep the generated ferrate, at a
certain temperature, to be used at a later time. The holding tank
may be at room temperature, or at a temperature that is either
higher or lower than room temperature. The mixture containing the
ferrate is then removed from the reaction chamber and is delivered
to the site of use. The site of use is "proximal" to the reaction
chamber.
[0069] In certain embodiments, as the mixture is removed from the
mixing chamber to the reaction chamber, additional iron salt and
oxidizing agent is added to the mixing chamber. In other
embodiments, additional iron salt and oxidizing agent is added to
the mixing chamber after all of the mixture within the mixing
chamber has been transferred to the reaction chamber. It is
contemplated in some of the embodiments of the present invention
that the flow of the mixture from the mixing chamber to the
reaction chamber is continuous. Therefore, while ferrate is needed,
new batches of the mixture are to be added to the mixing
chamber.
[0070] In some of the embodiments of the present invention, in
addition to the iron salt, a metal oxide is added to the mixture.
The metal oxide may be added at any point during the production of
ferrate, either as an original ingredient, or in the mixing
chamber, or in the reaction chamber, or anywhere along the path.
The metal oxide may also be added to a mixture comprising ferrate
subsequent to the production of ferrate, when ferrate is being
contacted, or after ferrate has been contacted, with the object to
be synthesized, cleaned, disinfected, oxidized, or coagulated. The
metal atom of the metal oxide may be a main group metal, a
transition metal, or an f-block metal. A "transition metal" is a
metal within columns 3-12 of the periodic table, i.e., metals in
the scandium, titanium, vanadium, chromium, manganese, iron,
cobalt, nickel, copper, and zinc triads. An "f-block metal" is a
metal in the lanthanide or actinide series, i.e., metals with
atomic numbers 57-71 and 89-103. Thus, lanthanum and actinium are
both transition metals and f-block metals. The metal oxide may be
scandium oxide, titanium oxide, vanadium oxide, manganese oxide,
cobalt oxide, nickel oxide, copper oxide, zinc oxide, gallium
oxide, yttrium oxide, zirconium oxide, niobium oxide, molybdenum
oxide, ruthenium oxide, rhodium oxide, palladium oxide, silver
oxide, cadmium oxide, indium oxide, tin oxide, hafnium oxide,
tantalum oxide, tungsten oxide, rhenium oxide, osmium oxide,
iridium oxide, platinum oxide, or any salt containing the oxides of
these metals.
[0071] In certain embodiments, the solution comprising ferrate is
irradiated with light before or during use. In other embodiments,
the solution comprising ferrate is kept in the dark before use.
When the solution is irradiated with light, the light may be a
light of any frequency within the electromagnetic spectrum, i.e.,
anywhere between radio waves and x-rays and gamma radiation,
including ultraviolet light, visible light, or infrared light.
[0072] Certain other embodiments of the present invention are
directed to a "batch process," during which ferrate is generated
once. Thus, these embodiments of the present invention are directed
to a method of synthesizing ferrate, comprising adding an aqueous
solution comprising an iron salt and an oxidizing agent in a mixing
chamber; mixing the aqueous solution; delivering at least a portion
of the aqueous solution to a reaction chamber; and delivering at
least a portion of the ferrate to a site of use that is proximal to
the reaction chamber.
[0073] In certain embodiments, the ferrate generated by the above
method in the mixing chamber is delivered to the site of use
without being delivered to a separate reaction chamber. In these
embodiments, therefore, the mixing chamber and the reaction chamber
are one and the same. In certain other embodiments, after the
mixing in the mixing chamber, the ferrate solution is delivered to
a holding tank where it is kept until its use is needed. In any
event, the ferrate solution is held for a period of time that is
less than or equal to the half-life of the ferrate in the solution
under the conditions (i.e., temperature, concentration, pH, etc.)
it is held.
B. Solid State Production
[0074] In another aspect, the invention relates to a method of
continuously synthesizing ferrate, comprising providing a mixture
of an iron salt and an oxidizing agent; continuously delivering at
least a portion of the mixture to a heating chamber; exposing the
mixture to elevated temperatures in the heating chamber, thereby
generating ferrate; removing at least a portion of the generated
ferrate from the heating chamber; adding additional mixture to the
heating chamber.
[0075] In certain embodiments, the exposure of the mixture to
elevated temperatures and the removal of ferrate from the exposure
is continuous.
[0076] In some embodiments, the additional mixture added to the
heating chamber is in an amount to substantially replace the
portion of the ferrate removed from the heating chamber.
[0077] By "continuously delivering" it is meant that once the
mixture of iron salt and oxidizing agent begins to be delivered to
the heating chamber, it continues to be delivered to the heating
chamber for the duration of time that the method is being
practiced.
[0078] In certain embodiments of the invention, a base, as
described herein, is also added to the mixture.
[0079] In some of the embodiments of the present invention, the
mixture of the iron salt and the oxidizing agent is carried through
the heating chamber on a belt. The belt is made of materials that
can withstand temperatures higher than room temperature. These
materials may include, but not be limited to, rubber, steel,
aluminum, glass, porcelain, etc.
[0080] In certain embodiments of the invention the mixture is
poured directly onto the belt, whereas in other embodiments, the
mixture is poured into containers and the containers are placed on
the belt. In any of these embodiments, the surface that comes to
contact with the mixture is not reactive towards ferrate or other
oxidants.
[0081] The heating chamber is heated to temperatures higher than
room temperature. "Room temperature" is about 20.degree. C. In some
embodiments the heating chamber is heated to a temperature of
between about 20.degree. C. and about 1000.degree. C., or between
about 50.degree. C. to about 500.degree. C., or between about
100.degree. C. to about 400.degree. C. By "about" a certain
temperature it is meant that the temperature range is within
40.degree. C. of the listed temperature, or within 30.degree. C. of
the listed temperature, or within 20.degree. C. of the listed
temperature, or within 10.degree. C. of the listed temperature, or
within 5.degree. C. of the listed temperature, or within 2.degree.
C. of the listed temperature. Therefore, by way of example only, by
"about 400.degree. C." it is meant that the temperature range is
400.+-.40.degree. C. in some embodiments, 400.+-.30.degree. C. in
some embodiments, 400.+-.20.degree. C. in some embodiments,
400.+-.10.degree. C. in some embodiments, or 400.+-.5.degree. C. in
other embodiments, or 400.+-.2.degree. C. in still other
embodiments. In some embodiments the temperature remains relatively
constant throughout the process whereas in other embodiments the
temperature varies during the process. In the embodiments where the
temperature varies, the temperature may be ramped up, i.e., the
final temperature is higher than the initial temperature, or ramped
down, i.e., the final temperature is lower than the initial
temperature.
[0082] Thus, in some embodiments of the present invention, a
mixture of an iron salt and an oxidizing agent is put on a belt.
The iron salt and the oxidizing agent may be pre-mixed prior to
addition to the belt, or they may be mixed subsequent to addition
to the belt. The mixture may be added directly onto the belt or may
be added to containers that are placed on the belt. The mixture may
be added to the containers before the containers are put on the
belt or the mixture may be added to the containers while the
containers are on the belt. In certain embodiments, base is also
added to the mixture at some point.
[0083] The belt then moves through a heating chamber, thereby
heating the mixture. The heat must be sufficient to produce ferrate
in the mixture. The speed of the belt through the heating chamber,
the length of time the mixture is heated, and the temperature to
which the mixture is heated are all adjustable. Thus, the mixture
may be heated for seconds or for hours.
[0084] Subsequent to the heating event, the heated mixture, now
comprising ferrate, is removed from the belt. The belt then returns
to the original location for the addition of more of the mixture.
It is contemplated that the movement of the belt through the
heating chamber is continuous.
[0085] In some embodiments, the mixture exposed to elevated
temperature in the above method is a solid.
C. Electrochemical Production
[0086] In another aspect, the invention relates to a method of
continuously synthesizing ferrate, comprising providing an aqueous
solution comprising an iron salt in a reaction chamber, where the
reaction chamber comprises at least two electrodes; providing
sufficient electric current to the at least two electrodes to
convert at least a portion of the iron salt to ferrate;
continuously delivering at least a portion of the ferrate to a site
of use that is proximal to the reaction chamber; and adding
additional aqueous solution to the reaction chamber to
substantially replace the portion of the aqueous solution delivered
to the holding chamber.
[0087] By "continuously delivering" it is meant that once ferrate
begins to be delivered to the site of use, it continues to be
delivered to the site of use for the duration of time that the
method is being practiced.
[0088] In certain embodiments of the invention, base is added to
the aqueous solution, while in other embodiments, acid is
added.
[0089] The reaction chamber comprises two electrodes. The
electrodes are designed to conduct electricity through the aqueous
solution, thereby converting the iron of the iron salt to ferrate
in an electrochemical reaction. The iron of the iron salt may have
been added to the solution as an iron salt, or may be the dissolved
iron electrode, which became dissolved upon the introduction of
electricity. It is contemplated that as solution containing ferrate
is removed from the reaction chamber, additional aqueous solution
is added to the mixing chamber for additional reactions. In certain
embodiments, the flow of materials from the reaction chamber to the
holding chamber is continuous.
D. Other Examples of Methods of Ferrate Production
[0090] In one embodiment, ferric sulfate particles may be added to
a static mixer and mixed in an aqueous medium. The static mixer
includes a mixing mechanism that is capable of microparticulating
particles. Static mixers may be continuous radial mixing devices,
characterized by plug flow or any other conventional mixer. Static
mixers are preferred in that they have short residence times and
little back mixing. Thus, proper dosing of feed components with no
fluctuation in time is a prerequisite for good performance.
[0091] Another desirable feature of static mixers is that they have
no moving parts for mixing. The absence of moving parts and
reliance on surface area and conformation for reactant/product
movement reduces the need for coolant to cool the reaction. Thus,
static mixers are comparatively low maintenance pieces of
equipment. The static mixers used in the processes of the present
invention may be incorporated into pump-around loop reactors or in
cascade type reactors, such as those manufactured by Koch, i.e.,
The Koch-SMVP packing/Rog 92/. Other static mixers include Koch
type SMF, SMXL-R, SMXL, SMX and SMV type.
[0092] For other embodiments, a micro reactor is used for mixing
reactants. Micro-reactors and static mixers are usable to make
ferrate in a continuous process or a semi-continuous process.
[0093] The mixing mechanism may be a tortuous path, a mixing device
or an aspirator. Oxone or Caro's Acid or other strong oxidant in
container is added to the static mixer. The term "oxone" as used
herein refers to potassium peroxymonopersulfate or potassium
monopersulfate. Reaction begins instantaneously and generates heat.
The temperature of the reaction is adjusted through the use of a
cooling coil or cooling jacket to a temperature of about
-10.degree. C. Temperature is controlled through a feed forward
feed back control mechanism. Water is employed as a transport
medium for transporting the ferric sulfate, oxidant and reaction
products. The volume of the water is minimized to a volume that
maximizes ferrate production yield.
[0094] An amount of dry KOH may be added that is effective to
maximize ferrate production. The KOH is added to another micro
mixer or static mixer KOH is added to a main reactor. The KOH is
cooled to about -10.degree. C. prior to introduction to the main
reactor. The main reactor is also a static mixer.
[0095] An excess of KOH prevents conversion of Fe(III) to ferrate.
The use of static mixers maximize surface area available for
reaction for all of the reactants. It is believed that the use of a
static mixer or micro mixer speeds up the reaction process.
[0096] A use of Caro's acid is preferred in that it aids in
stabilizing ferrate because sulfate from the Caro's acid "buffers"
the ferrate. It is understood, however, that if the static mixer is
positioned proximal to water or wastewater to be treated, sulfate
stabilization is optional and Fe(0) oxidation can occur with
another oxidant, such as chlorine or peroxide.
[0097] The temperature in the reactor is preferably maintained at
about 40.degree. C., but may be as low as 20.degree. C. or as high
as 60.degree. C. As products are removed from the reactor, the
temperature in the product stream is gradually decreased to room
temperature.
[0098] A use of a static mixer permits a method of water treatment
that includes shocking an iron moiety with an oxidant, quenching
the reaction with KOH and injecting the ferrate into a water or
wastewater or sludge stream. The use of a static mixer renders a
complex chemical reaction performable by operators of water and
waster treatment plants. Because of the microparticulation of iron
species and very rapid mixing, conventional concerns about
temperature control are substantially eliminated.
[0099] In one other embodiment ferrate is produced in a continuous
process by hypochlorite oxidation of iron (III) in a strongly
alkaline solution and is precipitated by the addition of saturated
KOH. Hypochlorite used in ferrate synthesis is formed by
disproportionation of chlorine in a cold caustic soda solution:
Cl.sub.2+OH.sup.-.fwdarw.Cl.sup.-+OCl.sup.-+H.sup.+.
[0100] Ferrate ion may be produced by adding a material such as
ferric nitrate to the hypochlorite solution described:
10OH.sup.-+3OCl.sup.-+2Fe.sup.3+.fwdarw.2FeO.sub.4.sup.2-+3Cl.sup.-+5H.s-
ub.2O
[0101] Synthesis of ferrate begins by addition of KOH solutions to
a cold-water jacketed reactor set between 20.degree. C. and
40.degree. C. Gaseous or liquid chlorine is bubbled through the
liquid reaction mixture, and the solid iron salt or oxide is added.
Atmospheric pressure is maintained in the reactor. The ranges of
mole ratios of reactants, Cl.sub.2, KOH, Fe(III), are
1.5-30:10-60:1. The smaller ratios decrease product yields, while
the larger ratios require larger recycle streams back to the
reactor, leave KOH unused, or accelerate ferrate decomposition.
[0102] The average residence time of the ferrate in the reactor is
180 minutes. Residence times greater than 30 minutes lead to
significant ferrate decomposition. The product mixture leaving the
reactor is typically 2-6% potassium ferrate by weight.
[0103] The reaction mixture includes solid K.sub.2FeO.sub.4, KCl,
and Fe(OH).sub.3 and aqueous KOH, KOCl, KCl, and a small amount of
K.sub.2FeO.sub.4. The KOH concentration in this mixture is
increased to 35-45% by weight to further precipitate the ferrate
from solution. The temperature is lowered during this process to
5-20.degree. C. to maximize the yield of solid potassium ferrate.
The crude solid product is separated by centrifugation within 5
minutes of finishing the KOH addition and the liquids are recycled
back to the reactor.
[0104] The crude product is contaminated with KCl and Fe(OH).sub.3.
Selectively dissolving the potassium ferrate into 10-20% KOH (aq),
by weight, at 20-50.degree. C., purifies the product. The KCl and
Fe(OH).sub.3 are insoluble in this media and are removed by
centrifugation. The solids may be separated and reprocessed for use
as starting materials in ferrate production.
[0105] The ferrate ion may be reprecipitated by addition of
concentration KOH solutions, 40-55% by weight, or solid KOH. When
the resulting mixture is 30%, crystals of K.sub.2FeO.sub.4
precipitate when the solution is cooled to between -20 and
0.degree. C. As in the earlier separation steps, the solid is
collected by centrifugation. The separated KOH solutions may be
recycled to the ferrate reactor.
[0106] The potassium ferrate produced may be washed in a tank with
anhydrous DMSO to remove any entrapped KOH or water. The DMSO is
recovered by flash evaporation. Next, the solid is transferred to a
methanol wash tank for further purification. The solid is finally
collected by centrifugation. The methanol is recovered by
distillation.
[0107] In another embodiment reactants described above are added to
a reactor cooled to a temperature of 20.degree. C. After about 180
minutes, reaction products are treated with KOH, to solubilize any
precipitated ferrate and the entire mixture is transferred to water
or wastewater or sludge for treatment. For one embodiment, effluent
from the reactor includes unreacted ferric sulfate, unreacted
oxone, potassium sulfate, KOH and about 20% dissolved ferrate. The
presence of KOH and ferric ions retard the decomposition rate with
water as the product stream is being mixed with untreated
water.
[0108] The mixture containing the ferrate may be polished, if
required.
[0109] In another embodiment hypochlorite is substituted for
chlorine gas. By introducing NaCl to the reaction mixture,
Na.sub.2FeO.sub.4 is precipitated without any need for a KOH
leaching step or extra equipment.
[0110] In another embodiment ferrate is generated as a solid in a
fluidized bed reaction. The fluidized bed comprises one or more of
FeCl.sub.2, FeSO.sub.4, Fe.sub.2(SO.sub.4).sub.3,
Fe(NO.sub.3).sub.3 and beta-ferric oxide monohydrate, oxygen gas
and chlorine gas. The reaction occurs at a reduced temperature,
such as 20.degree. C. Crystals of ferrate are produced.
[0111] In one other embodiment ferrate is produced as a result of a
direct reaction of alkali peroxides, such as sodium peroxide or
potassium peroxide or potassium superoxide with hematite to produce
potassium or sodium ferrate. The reaction is believed to proceed by
these chemical reactions:
##STR00001##
[0112] The temperature of reaction for this synthetic approach is
about 400 to 600.degree. C. for a time of about 12 hours. It is
believed that chemical reaction occurs though a solid-solid
contact, a liquid-solid contact or a vapor/solid contact. The
liquid is a molten salt. The vapor is a material such as
K.sub.2O.sub.2 vapor.
[0113] Reactants should be dry, of fine particle size and well
mixed. Mixing should avoid contact with air, as moisture and
CO.sub.2 will react with peroxide. Reactants should be held at 120
to 150.degree. C. in a TGA in dry nitrogen to thoroughly remove any
adsorbed water prior to heating to the TGA reaction
temperature.
[0114] When dissolved peroxide/superoxide reacts with hematite, it
produces ferrate, dissolved in a salt solution. Upon cooling, the
dissolved ferrate ions precipitate from the salt as crystals of
K.sub.2FeO.sub.4. A high temperature route produces
K.sub.2FeO.sub.4, but with modest yields and with a requirement of
a subsequent processing step to separate the K.sub.2FeO.sub.4 from
the salt mixture. In one embodiment, the salt mixture is not
separated and the entire mixture is used for water or wastewater
treatment. One advantage is that a simple process involving a
single high temperature reactor translates into a lower cost of
production.
[0115] One other option is a two-step process. An inexpensive
source of peroxide/superoxide is processed in a first reactor to
produce a gas stream containing peroxide/super oxide species. The
gas stream is ducted into a second reactor containing hematite,
where a direct reaction is carried out to produce ferrate. The
temperatures of reactors A and B are separately set to optimize
respective processes. With this process, the first reactor
temperature is about 1000.degree. C. and the second reactor
temperature is 400-500.degree. C. The peroxide reaction may be
performed in a static mixer as described for a reaction of iron and
Caro's acid.
[0116] While oxidants of oxone, Caro's acid, peroxide/superoxide,
chlorine and hypochlorite are described herein, it is understood
that other oxidants may be suitable for use. Some of these oxidants
are described in an article on ferrate oxidants in Grazzino
Italiano by Losanna. It is believed that enzymes may also be usable
in ferrate process embodiments of the present invention to reduce
reaction temperature.
III. DEVICE FOR ON-SITE GENERATION OF FERRATE
A. Solution Phase Production Device
[0117] In another aspect, the invention relates to a device for
continuously synthesizing ferrate for delivery to a site of use,
comprising a first holding chamber; a second holding chamber; a
mixing chamber controllably connected to the first holding chamber
and to the second holding chamber, into which a content of the
first holding chamber and a content of a second holding chamber are
added to form a first mixture; a reaction chamber controllably
connected to the mixing chamber, the reaction chamber adapted to
receive the first mixture and maintain the first mixture for a
period of time; a ferrate mixture in the reaction chamber; and an
output opening in the reaction chamber through which the ferrate
mixture is adapted to be transported to the site of use, where the
site of use is proximal to the reaction chamber.
[0118] In some embodiments the mixing chamber further comprises a
mechanical agitator.
[0119] In other embodiments, the mixing chamber comprises a tube
configured to mix the mixture as it passes through the tube.
[0120] Certain embodiments of the invention relate to a device in
which the mixing chamber further comprises a temperature control
device. The temperature control device may include a jacket around
the mixing chamber whereby a cooled or heated fluid is passed
through the jacket in order to maintain the temperature of the
intraluminal space at a certain pre-determined level.
[0121] Other embodiments of the invention further comprise a pump
downstream from the first and the second holding chambers and
upstream from the mixing chamber. The pump controls the flow of
materials into the mixing chamber.
[0122] Some other embodiments of the invention further comprise a
pump downstream from the mixing chamber and upstream from the
reaction chamber. This pump controls the flow of material out of
the mixing chamber and into the reaction chamber.
[0123] In some of the embodiments of the invention the reaction
chamber comprises a tube located between the mixing chamber and the
output opening.
[0124] In another aspect the invention relates to a system for
continuously synthesizing ferrate, comprising a first holding
chamber containing an iron salt; a second holding chamber
containing an oxidizing agent; a mixing chamber controllably
connected to the first holding chamber and to the second holding
chamber, into which the iron salt and the oxidizing agent are
controllably added to form a mixture; a reaction chamber
controllably connected to the mixing chamber, into which the
mixture is kept for a period of time, and in which ferrate is
synthesized, and an output opening in the reaction chamber through
which the ferrate may be transported to a proximal site of use.
[0125] In some embodiments a base, as described herein, is added to
the mixture. The iron salt, the oxidizing agent, the mixing
chamber, and the reaction chamber are as described herein.
[0126] In certain embodiments, the device of the invention further
comprises a pump downstream from the first and the second holding
chambers and upstream from the mixing chamber. In other
embodiments, the device further comprises a pump downstream from
the mixing chamber and upstream from the reaction chamber.
[0127] FIG. 1 shows an embodiment of the solution state production
device. The figure depicts two holding chambers 101. Other
embodiments of the invention may exhibit additional holding
chambers, depending on the number of ingredients added initially.
Some embodiments of the invention may exhibit only one holding
chamber 101. The holding chambers are connected to the mixing
chamber 103. In some embodiments, the flow of material between the
holding chambers 101 and the mixing chamber 103 may be controlled.
The flow is controlled either by the presence of a pump or a valve
(107) after each holding chamber 101, or by the presence of a pump
or a valve (109) before the mixing chamber 103, or by a combination
thereof. In certain embodiments, no pump or valve exists between
the holding chamber 101 and the mixing chamber 103.
[0128] The mixing chamber 103 is connected to the reaction chamber
105. In some embodiments, the flow of material between the mixing
chamber 103 and the reaction chamber 105 may be controlled. The
flow may be controlled by the presence of a pump or a valve (111)
after the mixing chamber 103. In certain embodiments, no pump or
valve exists between the mixing chamber 103 and the reaction
chamber 105.
[0129] The reaction chamber 105 is connected with an output opening
115, through which the product of the reaction is transferred to
the site of use. The flow from the reaction chamber 105 to the
output opening 115 may be controlled. The control may be through
the use of a pump or a valve (113). In certain embodiments, no pump
or valve exists between the reaction chamber 105 and the output
opening 115.
[0130] As depicted in FIG. 1A, in certain embodiments, the holding
chambers 101 connect to the mixing chamber 103 via a single pipe,
i.e., there is a T-junction before the mixing chamber 103. However,
as depicted in FIG. 1B, in certain other embodiments, each holding
chamber 101 is separately connected to the mixing chamber 103.
[0131] In some embodiments, the device of the present invention
also features a temperature control unit. The temperature control
unit controls the temperature of the holding chambers 101, the
mixing chamber 103, the reaction chamber 105, or a combination
thereof, or the temperature of the entire device. These components
may be held at room temperature, at a temperature above room
temperature, or at a temperature below room temperature, depending
on the reaction conditions and the needs of the particular use
contemplated. In some embodiments, different parts of the device
are held at different temperatures, thus, requiring more than one
temperature control unit for the device.
[0132] In certain embodiments, the mixing chamber 103 may just be a
pipe or a hose connecting the holding chambers 101 to the reaction
chamber 105. In some other embodiments, the reaction chamber 105
may just be a pipe or a hose connecting the mixing chamber 103 to
the output opening 115. Therefore, in one embodiment of the
invention, the entire device will comprise of a pipe or a hose
connecting the holding chambers 101 to the output opening 115.
B. Solid State Production Device
[0133] In another aspect, the invention relates to a device for
continuously synthesizing ferrate, comprising a holding chamber; a
mover controllably connected to the holding chamber such that at
least a portion of a content of the holding chamber is transferred
to the mover; a heating chamber, through which at least a portion
of the mover moves; an output opening in the heating chamber
through which the content on the mover is adapted to be transported
to a site of use, where the site of use is proximal to the heating
chamber.
[0134] In certain embodiments, the mover comprises a conveyor belt.
The belt is made of materials that can withstand temperatures
higher than room temperature. These materials may include, but not
be limited to, rubber, steel, aluminum, glass, porcelain, etc.
[0135] Some of the embodiments of the invention relate to a device
that further comprises a mixer between the holding chamber and the
mover.
[0136] In other embodiments, the heating chamber further comprises
a temperature control device.
[0137] Other embodiments of the invention relate to a device that
further comprises a storage chamber after the output opening in the
heating chamber. Therefore, the conveyor belt may deposit the
heated mixture into this storage chamber following the heating
event.
[0138] One embodiment of the device of the present invention is
depicted in FIG. 2. Starting materials are added to holding
chambers 201. Some embodiments of the invention exhibit only one
holding chamber 201, while others exhibit two or more holding
chambers 201. The starting materials are then combined and added to
a belt 203 that carries the starting materials through a heating
chamber 205. The starting materials may be combined prior to their
placement on the belt 203, or may be mixed on the belt 203 after
they have been placed there separately.
[0139] The embodiment depicted in FIG. 2 shows that the holding
chambers empty their contents into a single pipe which in turn
empties the starting material through opening 211 onto the belt
203. However, in other embodiments, each holding chamber may
separately empty its contents onto the belt 203.
[0140] In some embodiments, the flow of material between the
holding chambers 201 and the belt 203 may be controlled. The flow
is controlled either by the presence of a pump or a valve (207)
after each holding chamber 201, or by the presence of a pump or a
valve (209) before the opening 211, or by a combination thereof. In
certain embodiments, no pump or valve exists between the holding
chamber 201 and the opening 211.
[0141] In certain embodiments, the starting materials are added
directly onto the belt 203. However, in other embodiments, the
starting materials are added into containers that are placed on the
belt. Starting materials may be added into the containers before
positioning the containers on the belt, or the containers may be
positioned on the belt before the starting materials are added.
[0142] The heating chamber 205 comprises a heating unit that can
heat the temperature within to above room temperature. Various
heating units are known in the art. In FIG. 2, the heating chamber
205 is depicted as a cylinder, though those of skill in the art
realize that the heating chamber may have any shape, such as a cube
or a sphere or the like. The heating unit 205 may also exhibit a
temperature control unit.
[0143] The speed with which the belt travels through the heating
unit, the length of the heating unit, and the temperature of the
heating unit can be controlled by the operator in order to ensure
that the necessary yield of ferrate is achieved. Therefore, the
device of the present invention may exhibit a quality control
device at the exit end of the heating unit (213) that can determine
the yield of ferrate in the mixture. The quality control device may
be a chemical sensor, a photochemical sensor, a spectrophotometer,
or the like. The quality control device may be connected to a
computer that can control the speed of the belt through the heating
unit and/or the temperature of the heating unit. Therefore, if the
yield of ferrate is too low, the device may automatically decrease
the speed of the belt and/or increase the temperature of the
heating unit. Similarly, if the yield of ferrate is too high, the
device may automatically increase the speed of the belt and/or
decrease the temperature of the heating unit. In other embodiments,
the quality control device issues a signal to the operator of the
device, where the operator may manually adjust the speed of the
belt and/or the temperature of the heating unit.
[0144] At the exit end of the heating unit 213, ferrate is removed
from the belt 203 and is delivered to the site of use. In some
embodiments, ferrate just falls off the belt 203 and into a
receiving chamber 217, where it can be delivered to the site of use
through the opening 215. In other embodiments, where ferrate is in
a container, the container is removed from the belt and the
contents thereof are emptied into the receiving chamber, either
manually or automatically.
[0145] After removing the ferrate from the belt 203, the belt 203
then loops around to receive more ferrate and repeat the
process.
C. Electrochemical Production Device
[0146] In another aspect, the invention relates to a device for
continuously synthesizing ferrate, comprising a reaction chamber
comprising at least two electrodes and a solution of an iron salt,
where the electrodes provide sufficient electric current to convert
the solution of an iron salt to a solution of ferrate; a holding
chamber controllably connected to the reaction chamber, into which
the solution of ferrate is kept for a period of time; and an output
opening in the holding chamber through which the mixture is adapted
to be transported to a site of use, where the site of use is
proximal to the holding chamber.
[0147] In some embodiments the reaction chamber further comprises a
mechanical agitator.
[0148] In other embodiments the reaction chamber comprises a tube
configured to mix the mixture as it passes through the tube.
[0149] In certain other embodiments the reaction chamber further
comprises a temperature control device.
[0150] Some other embodiments of the invention further comprise a
pump downstream from the reaction chamber and upstream from the
holding chamber. This pump controls the flow of material out of the
reaction chamber and into the holding chamber.
[0151] In some of the embodiments of the invention the holding
chamber comprises a tube located between the reaction chamber and
the output opening.
[0152] One embodiment of the device of the present invention is
depicted in FIG. 3. The figure depicts a holding chamber 301. Other
embodiments of the invention may exhibit additional holding
chambers, depending on the number of ingredients added initially.
Some embodiments of the invention may exhibit two or more holding
chambers 301. The holding chamber is connected to the reaction
chamber 303. In some embodiments, the flow of material between the
holding chamber 301 and the reaction chamber 303 may be controlled
by the presence of a pump or a valve (307) after the holding
chamber 301. If there are more than one holding chambers 301, then
the flow may be controlled either by the presence of a pump or a
valve (307) after each holding chamber 301, or by the presence of a
pump or a valve before the reaction chamber 303, or by a
combination thereof. In certain embodiments, no pump or valve
exists between the holding chamber 301 and the reaction chamber
303.
[0153] The reaction chamber 303 comprises at least two electrodes
321. The electrodes are connected via wires 319 to a power source
317. The power source 317 may be an AC or a DC power source. The
electrodes 321 and the power generated by the power source 317 are
such that they are able to electrochemically oxidize iron, in any
oxidation state below +4, to ferrate. In some embodiments, one of
the electrodes is an iron electrode, which serves as both an
electrode and as the source of iron for the production of ferrate.
If the electrode is an iron electrode, there may or may not be a
need for having a holding chamber 301 in the device. An "iron
electrode" includes any electrically conducting material comprising
iron.
[0154] The reaction chamber 303 is connected with an output opening
315, through which the product of the reaction is transferred to
the site of use. The flow from the reaction chamber 303 to the
output opening 315 may be controlled. The control may be through
the use of a pump or a valve (313). In certain embodiments, no pump
or valve exists between the reaction chamber 303 and the output
opening 315.
[0155] In certain embodiments, there is a second holding chamber
305 between the reaction chamber 303 and the output opening 315.
The second holding chamber may serve as a storage place for the
generated ferrate between the time of its generation and the time
of its use. The flow between the reaction chamber 303 and the
second holding chamber 305 may be controlled through the use of a
pump or a valve (311).
[0156] In some embodiments, the device of the present invention
also features a temperature control unit. The temperature control
unit controls the temperature of the holding chambers 301, the
reaction chamber 303, the second holding chamber 305, or a
combination thereof, or the temperature of the entire device. These
components may be held at room temperature, at a temperature above
room temperature, or at a temperature below room temperature,
depending on the reaction conditions and the needs of the
particular use contemplated.
IV. PURIFICATION/SEPARATION OF FERRATE
[0157] The ferrate produced by the methods of the present invention
may be used without substantial purification. By "substantial
purification" it is meant a purification step that brings the
purity of the ferrate in the solution to greater than 99%, that is,
a substantially pure ferrate solution is a solution in which more
than 99% of the solutes comprise ferrate and its counter-ion.
[0158] However, the ferrate solution generated by the methods of
the present invention may be somewhat purified or undergo a
separation step. For example, the ferrate solution may be filtered
to remove undissolved solids. The filtration may be physical
filtration, in which particles that are too big to pass through the
filter pores are removed, or surface filtration, where the
particles are captured on the surface of filter grains, or a
combination of one or more filtration processes.
[0159] Ferrate may also be purified using ion exchange
purification. In this process, ferrate ions are reversibly bound to
a solid state material, the column is purged of unwanted
impurities, and then the ferrate is released from the column. The
solid state material of the ion exchange column may be any of the
solid state materials currently used, or designed later, for this
purpose, and include without limitation, clays, zeolites,
phosphonates, titanates, heteropolyacid salts, layered double
hydroxides, inorganic resins, organic resins, and gel-type
exchangers (e.g., as small beads in several mesh sizes), and
carbon-based inorganic exchangers. Additionally, inorganics can be
incorporated into organic resins to make composite exchangers for
purifying ferrate.
[0160] Membranes used for purification of ferrate may be made of
materials such as organic polymeric materials. The membrane
materials can be cellulose or polyamide (for example, fully
aromatic polyamide TFC membranes). Other membranes include, but are
not limited to, microfiltration, ultrafiltration, and inorganic
nanofiltration membranes. These membranes are generally made from
glass, ceramics, or carbon.
[0161] Ferrate may also be purified in a direct electric field
technique, during which a direct current electric field is applied
across a pair of electrodes. The ferrate ions in the liquid phase
are moved under the action of the field to a desired location where
they are pumped out for use. The ferrate transport under the action
of an electric field can be electromigration, electroosmosis, or
electrophoresis.
[0162] The ferrate solution produced by the methods of the present
invention may also be stored in a sedimentation tank for a period
of time and the supernatant then decanted or pumped out. The
ferrate solution may also pass through a centrifuge where the
solution is spun such that the heavier particles in the solution
sink to the bottom and the supernatant, comprising purified
ferrate, is removed for further use.
[0163] In certain other embodiments, the ferrate produced by the
methods of the present invention is encapsulated in a membrane for
future use. The membrane may be molecular sieves, clay, porcelain,
or other porous material that are not susceptible to oxidation by
ferrate. Then, to use the ferrate, at least a portion of the
membrane is contacted with the aqueous or gaseous mixture to be
treated.
[0164] The membrane may also be slightly water soluble so that as
portions of it are dissolved away, more ferrate is exposed to the
aqueous mixture to be treated. In this embodiment, the use of
ferrate may be in a time-release manner, the time of the release
being defined by the solubility of the layers of the membrane.
[0165] The devices disclosed herein may also feature a purification
component that purifies ferrate consistent with the purification
methods described herein.
V. USES OF FERRATE
[0166] In another aspect, the invention relates to a method of
treating, at a site of use, an aqueous mixture having one or more
impurity, comprising continuously generating ferrate in a reaction
chamber located proximal to the site of use; contacting the ferrate
with the aqueous mixture at the site of use, whereby at least a
portion of the impurity is oxidized.
[0167] In certain embodiments, the impurity is selected from the
group consisting of a biological impurity, an organic impurity, an
inorganic impurity, a sulfur-containing impurity, a
nitrogen-containing impurity, a metallic impurity, and a
radioactive impurity, or a combination thereof. Other impurities
are as described herein.
[0168] An "impurity" is defined to be any component of a solution
or a system, whose presence within that solution or system is
repugnant to the contemplated use of that solution or system.
Biological impurities are those that have a biological origin.
Thus, any cells, bacteria, viruses, tissues, etc., or components
thereof, whether from plants or animals, are considered to be
biological impurities. Organic impurities are chemical compounds
that contain at least one carbon atom. Inorganic impurities are
chemical compounds that contain no carbon atoms. A
sulfur-containing impurity is one which contains at least one
sulfur atom. A nitrogen-containing impurity is one which contains
at least one nitrogen atom. A metallic impurity is one which
contains at least one metal atom, whether main group metal,
transition metal, or f-block metal. A radioactive impurity is one
which undergoes radioactive decay, whether by emitting .alpha.,
.beta., or .gamma. particles. Those of skill in the art recognize
that a particular impurity may fall within more than one category
listed above. For example, calcium ethylenediamine tetra-acetate
(EDTA) impurity in water is an organic impurity, a
nitrogen-containing impurity, and a metal-containing impurity.
[0169] The ferrate for use in the treatment method is produced by
one of the methods set forth herein, i.e., the chemical production,
the solid state production, or the electrochemical production.
[0170] The ferrate produced by the above methods is contacted with
the aqueous mixture to be treated. In some embodiments the
contacting step comprises adding the ferrate to a stream of the
aqueous mixture. In other embodiments, the contacting step
comprises contacting the ferrate to a pool of the aqueous mixture.
In yet other embodiments the contacting step comprises contacting a
stream of the aqueous mixture with a stationary container
containing the ferrate.
[0171] Generally, the ferrate produced by the process of this
invention can be used in connection with any known process and for
any known purpose. The ferrate produced by the process of this
invention is especially useful as an oxidant, flocculent and/or
coagulant. In particular, potential uses of ferrate produced by the
process of this invention include the following: removal of color
from industrial electrolytic baths; manufacture of catalysts for
the Fischer-Tropsch process to produce reduced hydrocarbons from
carbon monoxide and hydrogen; purification of hemicellulose;
selective oxidation of alkenes, alkyl side chains, organic sulfur
compounds, thiols, sulfinic acids, organic nitrogen compounds,
carboxylic acids, halides, alcohols and aldehydes and in oxidative
coupling; as a general oxidant for water, waste water and sewage
treatment; disinfection as a biocide or virocide; phosphorylase
inactivator; anti-corrosion paint additive; denitration of flue
gas; electrodes for batteries; detoxification of cyanide and
thiocyanate from waste waters; oxygen demands measurement;
cigarette filters to remove HNC and carcinogenic molecules;
oxidizer for hazardous wastes and other waste solutions such as
from the pulp industries; pollution control in the removal of
hydrogen sulfide from low pressure gas streams; removal of
pollutants with mutagenic and carcinogenic characters such as
naphthalene, nitrobenzene, dichlorobenzene and trichloroethylene
from waste water and drinking water without coproduction of harmful
products; additive to cements as structural hardener; disinfectant
to inactivate E. coli, Salmonella, Shigella, and other fecal
coliform as a bacterial cell removal step; removing Streptococcus
and Staphylococcus; biofouling control with non-corrosive oxidant
for removal of slime films formed of microorganisms such as in
electric power plants and shipboard cooling systems; removal of
bacteria, heavy metals and inorganics in drinking water in an
oxidation coagulation processes; removal of hydrogen sulfide from
sour gas in the "Knox" process; delignification of agricultural
residues to produce glucose and ethanol from wheat straw; magnetic
filler of barium and strontium ferrate for flexible plastics having
high polymer binder contents; support for other oxidizers such as
chromium (VI) and KMnO.sub.4; denitrification of sinter furnace
off-gas; removal of impurities from solutions fed to zinc plants;
decontamination of waste waters containing cyanide and thiocyanate;
oxidative destruction of phenol, sulfite and thiosulfate; as a
catalyst in burning of coal to remove impurities in steam
gasification step; component of grinding wheels; etching agent in
fluid form for evaporated films; and ceramic encapsulated rare
earth metal ferrates for use in electronics where ferromagnetic
properties are needed. These and other applications are discussed
in Deininger, U.S. Pat. Nos. 5,202,108, 5,217,584, and 5,370,857,
all of which are incorporated herein by reference in their
entirety.
[0172] Additional uses of ferrate are discussed below.
A. Waste Water Treatment
[0173] As noted above, there is a need for development of safe,
inexpensive and "environmentally friendly" oxidants, especially for
water and wastewater treatment applications. The treatment of
industrial and municipal effluents containing hazardous organic and
inorganic compounds is an important research endeavor. Currently,
several methods for contaminant removal exist, including
adsorption, coagulation, biodegradation, chemical degradation, and
photodegradation. Chemical degradation is often the most
economically feasible as well as the easiest method for water
treatment and usually involves chlorine, hypochlorite, or ozone.
Although effective, these oxidants often have deleterious side
effects. Chlorine and ozone are poisonous and highly corrosive
gases.
[0174] Hypochlorite is generally supplied as a solid or in aqueous
solution; however, it is generated using chlorine gas and can
rapidly decompose back into chlorine upon heating or chemical
mishandling. Also, although hypochlorite, OCl.sup.-, is used as a
chlorine source for water treatment at smaller operations, it is
expensive.
[0175] Additionally, the handling of chlorine, or hypochlorite,
poses potential danger to workers due to its high toxicity. A major
disadvantage of chlorine and chlorine-containing oxidants is that
excess chlorine can produce chlorinated oxidation products (e.g.,
chloramines, chlorinated aromatics, chlorinated amines or
hydrocarbons), many of which are potential mutagens or carcinogens,
and may be more toxic than the parent contaminants and/or more
difficult to remove. Because these compounds potentially constitute
a health hazard for the public, a move away from chlorine use is
needed.
[0176] The ferrate produced by the methods of the present invention
may be used in treating waste water, sewage, or sludge. It is well
known in the art that ferrate reacts with organic or inorganic
compounds and biological entities, such as cells, bacteria,
viruses, etc. In this reaction, the substrates are oxidized to
biologically inactive products. The ferrate molecule itself is
reduced to Fe(III), which precipitates out of the solution as
Fe(OH).sub.3 or other Fe(III) salts. The iron containing salts can
be easily filtered out, leaving iron-free water containing
innocuous by-products.
[0177] Escherichia coli, Salmonella, and Shigella are all members
of the Enterobacteriaceae. These bacteria and certain others known
to those of skill in the art have similar physiological
characteristics, including being rod shaped gram-negative
facultatively anaerobic organisms. E. coli has long been used as an
indicator of fecal pollution in water systems and there is a large
volume of disinfection literature available for this particular
organism. Ferrate is an effective biocidal agent against suspended
bacterial cultures in clean systems. Ferrate has the capacity to
rapidly inactivate several known pathogens at fairly low
concentrations.
[0178] Ferrate is also an effective disinfectant against viruses,
such as the F2 virus. Ferrate has been studied for its antiviral
activities and has been found to be effective in inactivating
viruses (Kazama, Wat. Sci. Tech. 31(5-6), 165-168 (1995).) Ferrate
also coagulates turbidity in water system and inactivates most
enteric pathogens at ferrate concentrations which are reasonable
for use in a water and wastewater treatment facility.
[0179] The biocidal properties of ferrate have also been
investigated (Y. Yamamoto, Mizu Shori Gijutsu, Vol. 24, p, 929
(1983)). An important property of ferrate toward its application as
a water treatment agent is its ability to act as a potent biocide.
Ferrate has been used for disinfection in river water treatment, as
well as in municipal sewage treatment processes; with its use,
removal of coliform bacteria depends on the pH. It has been shown
to be effective against E. coli and sphaerotilus (F. Kazama, J.
Ferment. Bioeng., Vol. 67, p. 369 (1989)). Ferrate has also been
used to remove coliform bacteria from treated sewage and river
water (F. Kazama and K. Kato, Hamanashi Daigaku Kogakubu Kenkyu
Hokoku, Vol. 35, p. 117 (1984)).
[0180] In addition, ferrate can be used to oxidize ammonia in the
secondary effluent from water treatment plants. The major oxidation
product is nitrogen, while some nitrites are also present in the
products. Both of these oxidation products are environmentally
friendly.
[0181] The above properties of ferrate can be exploited at
municipal or industrial water treatment plants. A ferrate producing
device can be installed in close proximity of the water treatment
facility. Waste from the municipal sewer lines or the industrial
effluent lines is mixed with freshly produced ferrate on site. The
ferrate producing device can produce as much or as little ferrate
as is necessary to react with all the waste present in the
effluent.
[0182] Since ferrate is an efficient disinfectant, it has potential
for use in lieu of extensive chlorination of drinking water. As
pollution increases, the need exists for a water purifying agent
that can be safely used by the individual on "small" quantities of
drinking water as well as at the municipal/industrial wastewater
level. Such purification agents should ideally be able to disinfect
and remove suspended particulate materials, heavy metals (including
radioisotopes) and some organics through flocculation, in order to
at least partially destroy dissolved organic contaminants through
oxidation, and as a final step, to remove itself from solution. A
one-step purification reagent which meets these criteria is
FeO.sub.4.sup.2-, ferrate. This ion is able to successfully compete
with the current two-step, chlorination/ferric sulfate,
flocculation technique, thereby circumventing the production of
toxic or carcinogenic halogenated organics.
[0183] Since ferrate has multipurpose oxidant-coagulant properties,
it is very attractive for the treatment of waste produced by
chemical and pharmaceutical companies. These companies spend
billions of dollars a year in clean up costs for contaminated water
used, or produced, in their processes. Almost all of the waste
produced by these companies can be oxidized to relatively harmless
by-products by ferrate, leaving water that can be released to the
municipal sewage systems and be treated without any special care.
Thus, any company that produces waste water laced with organic,
inorganic, or biological impurities can install a ferrate producing
device at the end of its effluent line.
[0184] Municipal sewage systems suffer a special burden. They are
overloaded with any imaginable waste, most of which is organic or
biological. Once the large objects are filtered out, the sewer
facilities must deal with the soluble waste remaining behind.
Normally, waste water facilities filter the waste water through
activated charcoal or other filters that have an affinity for
organic compounds, or biologically treat the wastewater. These
processes are slow and costly. The slow response of these
facilities to the in-flow of wastewater often results in sewer
overflows during storms. In coastal communities this results in raw
and untreated sewage spilling into the ocean or lake nearby,
causing environmental damage. While oxidants may easily be used to
remove the unwanted waste rapidly, the oxidants currently available
on the market are either cost prohibitive, or produce by-products
that are at times more environmentally unsafe than the waste
itself
[0185] Also, there is a vital need for new methods for H.sub.2S
control in municipal sanitary sewer systems and treatment plants,
and industrial waste treatment facilities. One of the ongoing major
problems in waste water treatment is severe corrosion of facility
structures from contact with hydrogen sulfide gas, H.sub.2S, or its
oxidation products after contact with air. Equally important are
the health risks from exposure to H.sub.2S gas for even short
periods of time; such exposure is reported to be the leading cause
of death among sanitary sewer workers. Another major problem with
the evolution of H.sub.2S gas is its foul smell that causes
discomfort to those exposed to it.
[0186] Ferrate is known to be useful in a variety of waste water
treatment applications. Ferrate oxidations, and their application
to waste water treatment, have been studied with a view toward
using ferrates in several industrial applications, in particular
with a number of organic and inorganic substrates. (J. D. Carr, P.
B. Kelter, A. Tabatabai, D. Spichal, J. Erickson, and C. W.
McLaughlin, Proceedings of the Conference on Water Chlorination and
Chemical Environmental Impact Health Effects, pp. 1285-88 (1985)).
The applicability of ferrate in waste treatment involves not only
its oxidative abilities, but also other multipurpose properties,
such as its floc formation, disinfective properties, and generally
remediative faculties.
[0187] Direct filtration of ground water using ferrate has been
examined at the pilot plant level (T. Waite, Environ. Sci.
Technol., Vol. 17, p. 123 (1983)). Biofouling control has been
investigated (R. L. Bartzatt and D. Nagel, Arch. Env. Health, 1991,
Vol. 46(5), pp. 313-14 (1991)). The coagulative properties of
ferrate have been found to be useful for turbidity removal (S. J.
de Luca, C. N. Idle, A. C. Chao, Wat. Sci. Tech. 33(3), 119-130
(1996)). Studies have shown that when model condensers were dosed
with 10.sup.-5 M solutions of ferrate twice a day, for 5 minutes,
biofilm growth was inhibited (T. Waite, M. Gilbert, and C. Hare,
Water Tech/Qual., pp. 495-497 (1976)).
[0188] Ferrate oxidative destruction of nitrosamines, which are
potent carcinogens, in waste water has been reported (D. Williams
and J. Riley, Inorg. Chim. Acta, Vol. 8, p. 177 (1974)).
[0189] Relatively low ferrate doses have been found to profoundly
reduce the BOD (biological oxygen demand) and TOC (total organic
carbon) in domestic secondary effluents (F. Kazama and K. Kato,
Kogabkubu Kenkyu Kokou, Vol. 35, pp. 117-22 (1984)).
[0190] Ferrate can be employed for the treatment of mill effluent
and sewage sludge from municipal sources. Treatment at 125-1000 mg
of K.sub.2FeO.sub.4/L dose levels was found to significantly
decrease the chemical oxygen demand on manganese (COD.sub.Mn), due
to partial oxidation of the high molecular weight organics.
Decreases in the UV spectrum after treatment with ferrate have been
interpreted as removal of fulvic and humic acids within the
iron(III) coagulate produced when the ferrate was reduced (F.
Kazama and K. Kato, Kogabkubu Kenkyu Kokou, Vol. 34, pp. 100-4
(1984)).
[0191] Polyaminocarboxylates such as diethylenetriaminepentaacetate
(DTPA), ethylenediaminetetracetate (EDTA), and nitriloacetate (NTA)
are synthetic ligands that form stable complexes with most of the
metals and are used in a variety of industrial applications such as
photographic developing, paper production, and textile dyeing.
Ethylenediaminedisuccinic acid (EDDS) forms hexadentate chelates
with transition metals and is used in consumer products, e.g.,
washing powder. EDTA is a constituent of formulations for chemical
decontamination of the primary heat transport system of nuclear
power reactors. The presence of heavy metals, along with
polyaminocarboxylates has been reported at many US Department of
Energy (DOE) sites. These polyaminocarboxylates are either poorly
biodegradable (e.g., EDTA), associated with other safety regulatory
issues (e.g., NTA) or little effective (e.g., citrate). Ferrate can
be applied to degrade polyaminocarboxylates and
metal-polyaminocarboxylates to simple products.
[0192] Certain compounds are listed in the EPA Contaminant
Candidate List (CCL). These include diazion, disulfoton, fonofos,
terbufos, cyanazine, prometon, 1,2-diphenylhydrazine, nitrobenzene,
acetochlor, 2,4,6-trichlorophenol, and 2,4-dichlorophenol. These
compounds can be oxidized by ferrate.
[0193] The gasoline additive methyl tert-butyl ether (MTBE) is a
ubiquitous groundwater contaminant. The U.S. geological Survey
National Water Quality Assessment Program has identified it in 27%
of urban wells tested. A more recent survey indicated that between
5 and 10% of all community drinking wells in the United States have
detectable MTBE contamination. It persists in
petroleum-contaminated aquifers. MTBE in groundwater can be
oxidized to relatively non-hazardous compounds using ferrate.
[0194] Trichloroethene (TCE), a nonflammable solvent used in large
quantities in industry, is one of the most common organic ground
water contaminants and is classified as a "probable human
carcinogen." TCE is sequentially reduced to dichloroethene (DCE)
isomers, chloroethene (CE), and ethene. The use of ferrate in
remediating contaminated groundwater is attractive due to ease of
field implementation and the relatively low cost.
[0195] Highly chlorinated phenol derivatives, such as
pentachlorophenol (PCP) have been listed as a priority pollutant by
the United States Environmental Protection Agency. PCP is mainly
used as a wood preservative and general biocide. PCP is a suspected
carcinogen and its pyrolysis and combustion reaction products are
considerably more toxic than PCP itself. Ferrate can be utilized in
degradation of PCP.
[0196] Ferrate can also be applied to effluent streams from
agrochemical industry. One of the common products from an
agricultural industry, the herbicide trifluaraline is a
pre-emergent, cellular and nuclear division inhibitor. It is highly
toxic for humans. Ferrate can be applied to effluent streams of
agrochemical industry containing compounds such as
trifluraline.
[0197] Dyes present in wastewater, which originated from the
textile industry, are of particular environmental concern since
they give undesirable color to the waters. They are also generally
harmful compounds and can lead to toxic byproducts through
hydrolysis, partial oxidation, or other chemical reactions taking
place in the waste phase. The decolorization and degradation of
different classes of textile dyes from the textile industry can be
achieved using ferrate.
[0198] In pharmaceutical and fine chemical manufacturing, organic
transformations are routinely carried out using oxidizing agents
based on transition metal compounds. One of the biggest problem
areas in synthetic methodology is selective oxidations. For
example, the oxidation of alcohols carried out with Cr(VI) or
Mn(VII) lack specificity and selectivity. Ferrate is selective and
specific in these reactions. The nontoxic properties of the Fe(III)
byproduct makes ferrate an environmentally safe oxidant. Ferrate
can be utilized in organic synthesis, thereby reducing the
environmental impact of the oxidation processes and also reducing
their cost ("green chemistry").
[0199] Thiourea and its derivatives are known corrosion inhibitors
and are used as chemical complexing agents to clean scales
developed in industrial equipment, like boilers and nuclear
reactors. Because of the toxicity of thiourea to aquatic organisms,
the treatment of boiler chemical cleaning wastes (BCCWs) is
required before their disposal. Ferrate can easily remove thiourea
and its derivatives from BCCWs.
[0200] Oil refineries and coke processing plants generate sulfur
and cyanide containing compounds. These contaminants are toxic and
environmentally significant due to their offensive odor. In
addition, their presence may not be acceptable in the environment
due to their high oxygen demand. Ferrate can be applied to
petroleum industry effluents to eliminate odor related to sulfur
and cyanide containing compounds.
[0201] Drinking water supplies are sometimes plagued by odors
resulting from the presence of manganese(II). Manganese(II) causes
aesthetic problems such as colored water, turbidity, staining, and
foul taste. Manganese(II) can also accelerate biological growth
which further exacerbates odor problems. Mn(II) is removed by
oxidation of soluble Mn(II) with a ferrate to sparingly soluble
hydroxide and oxide solid phases, MnOOH(s) and MnO.sub.2(s),
respectively.
[0202] Decontamination of chemical warfare agents is required on
the battlefield as well as in pilot plants, and chemical agents
production, storage, and destruction sites. Ferrate can oxidize
chemical warfare agents such as VX
[O-ethyl-S-(2-diisopropylamino)ethylmethylphosphono-thioate], GD
(pinacolyl methylphosphonofluoridate), GB
(2-propylmethylphosphonofluridate), mustard gas
(2,2'-dichlorodiethyl sulfide), and HD [bis(2-chloroethyl)
sulfide]. Ferrate has many applications such as environmentally
friendly "hasty" decontamination on the battlefield where speed and
ease of application of the decontaminant is essential.
[0203] During recovery of natural gas and crude oil from offshore
and onshore production operations, produced waters are generated,
containing complexed mixtures of organic and inorganic materials.
Approximately, 12 billion barrels of produced water are produced in
the US annually. This large volume causes major environmental
problems. The water toxicity and organic loading generally
characterize the impact of produced water to the environment. The
treatment with ferrate can reduce the organic loading and acute
toxicity of the oil field produced water.
[0204] Water supplies containing arsenic compounds are a worldwide
health concern. Tens of thousands of people already show symptoms
of arsenic poisoning. A maximum of ten microgram/L of arsenic in
water is the threshold value recommended by the World Health
Organization and the European Community. Current removal procedures
are not adequate to meet criteria for ambient arsenic in water
supplies. Steps involving oxidation, adsorption, and precipitation
can be carried out by ferrate in removing arsenic from water.
[0205] In recent years, there has been increasing concern for the
presence of natural organic matter (NOM) in potable surface and
ground water supplies. One reason for concern is related to the
formation of disinfection byproducts (DPB's) from the treatment of
water by chlorination methods. Oxidation of NOM by chlorination
produces chlorinated hydrocarbons, many of which are known or
suspected carcinogens. Ferrate has excellent potential to serve as
an environmentally friendly remediation treatment for reducing
levels of DPB's in drinking water. This process would not form
toxic chlorinated organics and may also effectively mineralize NOM
to carbon dioxide, potentially eliminating the production of DPB's
entirely.
[0206] Ferrate solution can be used to develop a method for
protecting iron and steel castings from corrosion. This procedure
is based on the formation of ferric oxide from the decay of the
thin film of ferrate on the metal. In this procedure, a mixture of
alkaline metal ferrate and alkaline solution containing a reducing
agent is brought into contact with metal surfaces.
[0207] There are several disadvantages of using metal salts such as
alum, ferric chloride, and ferrous sulfate in removing solids from
a solution. First, binding of water to the metal ions creates a
gelatinous sludge with a high water content that increases
dewatering costs. Second, the water becomes more acidic after the
addition of salts, causing a decrease in the coagulant property of
the salt. Thirdly, the formation of metal-phosphate complexes
causes phosphate levels in the solution to decrease and, as a
result, phosphate becomes less available to bacteria. This upsets
the biological function of the system. Synthetic organic polymers
are used as common coagulants and flocculents to replace metal
salts. To achieve this end, a large quantity of polymer is
required, which makes the process expensive. There are also several
disadvantages to using a synthetic polymer. Synthetic polymers
release toxic materials into water due to solubility of polymers.
In addition, solubility is also greatly influenced by environmental
factors such as temperature and pH. Polymers are very sensitive to
the quality of water and also have little effect on BOD. A
combination of polymers and ferrate can be advantageous. This
combination can require less amount of coagulant and thus be
cost-effective. Polymer-ferrate complexes can be formed to
eliminate the toxicity from the solubility of polymers.
Polymer-ferrate complexes can also have multi-purpose properties
and can be less sensitive towards quality of water.
[0208] A ferrate producing device located at a waste water facility
will be useful in overcoming all of the above-described problems
faced by these facilities. The device of the present invention can
produce inexpensive ferrate rapidly. Ferrate can be injected into
the flow of waste water and mixed therewith, thereby oxidizing and
removing the unwanted waste. Ferrate oxidation of organic and
inorganic compounds results in environmentally safe by-products. In
addition, the iron containing salt by-products can easily be
filtered off and removed from the waste water. This eliminates the
need to repeatedly pass waste water through filters, activated
charcoal, or geological reactors, or incubating the waste water in
pools of anaerobic bacteria for digestion of the organic waste.
[0209] The on-site generation of ferrate removes two of the
problems associated with its use today: cost and instability.
Because ferrate is produced on site and can be applied immediately
after its production, little or no attention must be paid to the
fact that it is unstable. The ferrate is simply introduced into the
waste water before it has had a chance to decompose. In addition,
the application of ferrate requires no need for purification,
crystallization, or storage; therefore, the cost of its use is very
low. Furthermore, the ferrate produced by the device of the
invention requires lesser amounts of expensive feed stock.
B. Treatment of Recreational Water
[0210] The ferrate generated by the methods of the present
invention can be used in pool and spa applications. It is well
known that pools, Jacuzzis, and spas become polluted with organic
waste. The waste enters the water from the body of the swimmers or
by wind or insects. If left untreated, the water becomes turbid and
foul. Usual methods of treatment include the addition of oxidants
such as bleach and anti-bacterial or anti-fungal agents. These
treatments create unwanted side-effects. The oxidants that are left
in the water have an adverse effect on the skin of the swimmers
using the water. In addition, the oxidants create environmentally
harmful by-products, such as chlorinated hydrocarbons.
[0211] The device of the present invention can be fitted to any
swimming pool or Jacuzzi such that the ferrate produced by the
device is mixed with the water in a mixing chamber, whereby all the
organic waste is oxidized to innocuous products, the iron salts are
filtered away, and the clean water is re-introduced into the pool.
This represents a highly effective and cost-efficient method of
cleaning the pool water, since ferrate produced by the methods of
the present invention is less costly in the long run than
purchasing the numerous oxidants and anti-fungal chemicals
necessary to treat a pool.
C. Use in Processing Plants
[0212] Many processing plants generate aqueous streams comprising
biosolids such as proteins, carbohydrates, fats, and oils which
must be treated to remove the potentially valuable biosolids
products before the stream can be discharged from the plant. These
aqueous streams are often derived from food processing plants and
have solids contents of about 0.01% to 5% on a weight basis. This
invention provides a process for clarification of such streams,
whereby the solids are flocculated, and biosolids are optionally
separated from the solids. The biosolids can subsequently be used,
for example, in animal feeds.
[0213] As defined herein, to "flocculate" means to separate
suspended biosolids from a stream comprising biosolids, where the
biosolids become aggregated and separate to the top or bottom of
the stream in which the biosolids had previously been suspended.
Flocculation produces a flocculated material, which, if desired,
can be physically separated from the stream. In the present
invention, it is desirable to maximize the size of the flocculated
material in order to facilitate removal of this material from the
stream.
[0214] The process of this invention involves treating an aqueous
stream comprising biosolids by contacting the stream with ferrate.
The aqueous stream can be derived from any number of processes,
which generate such streams, such as from animal and vegetable
processing, including processing for non-food uses.
[0215] In the process of this invention, the aqueous stream to be
treated can be from any processing plant that produces an aqueous
stream comprising biosolids, such as food processing plants. For
example, animal slaughterhouses and animal processing plants and
other food processing plants may produce aqueous streams comprising
protein, fats and oil. Animal slaughterhouses and processing plants
include those for cattle, hogs, poultry and seafood. Other food
processing plants include plants for vegetable, grain and dairy
food processing plants for processing soybeans, rice, barley,
cheese, and whey; plants for wet-milling of starches and grains; as
well as breweries, distilleries and wineries. Biosolids present in
aqueous streams from these processes may include sugars, starches
and other carbohydrates in addition to protein, fats, and oils. For
example in processing soybeans, proteins are extracted into an
aqueous stream from which they are subsequently recovered. The
present invention is especially useful for treating streams from
animal processing, and more particularly, from poultry
processing.
[0216] While this invention is useful in conventional food
processing operations, which produce aqueous suspensions of
biosolids, it should be recognized that this invention is also
useful in treatment of aqueous suspensions of biosolids derived
from processing of food (animal or vegetable) materials, which may
have non-food end uses. For example, when separated and recovered,
proteins are useful in certain cosmetics and other skin care
formulations; starch has numerous non-food uses, including uses in
paper manufacture. Further still, this invention is useful to treat
in general, any aqueous stream comprising biosolids, which may
result from non-food processing operations. Moreover, though the
biosolids, as disclosed above, are generally suspended in a
substantially aqueous stream, the concentration of biosolids
dissolved in the stream depends on the properties of the stream or
the biosolids such as, for example, pH, salinity, or other
parameters.
[0217] The process of this invention involves treatment of an
aqueous stream containing biosolids, for example, proteins, to
reduce suspended solids (as measured by turbidity) and optionally
to separate the biosolids. The biosolids can be recovered for
subsequent use. It should be recognized that this process can
capture both suspended biosolids as well as soluble materials, such
as those present in blood and sugars.
[0218] The flocculated biosolids can optionally be separated from
the treated stream by conventional separation processes such as
sedimentation, floatation, filtering, centrifugation, decantation,
or combinations of such processes. The separated biosolids can
subsequently be recovered and used in numerous applications. It has
also been surprisingly found that the recovered biosolids from this
process have reduced odor when dry relative to those recovered from
a process using ferric chloride as part of a flocculating system.
The flocculated biosolids can be separated and recovered by known
techniques, such as those mentioned above.
E. Use in Radioactive Clean Up
[0219] The process of the present invention is also useful for the
precipitation of radioactive materials, particularly uranium,
dissolved in aqueous solutions. The dissolved radioactive materials
may be from a naturally flowing stream, or a uranium mining
operation water treatment plant. The water from the stream is
destined to be treated by a conventional city water treatment
facility for drinking and home use.
[0220] Ferrate has been proposed as a treatment agent for the
removal of radionuclides (transuranics) from waste water. To date,
the focus has been on the nuclear industry, where ferrate is used
to remove uranium and transuranic elements from contaminated water.
In addition, there is currently an interest in using ferrate in the
removal of plutonium and americium from waste water effluent.
[0221] U.S. Pat. No. 4,983,306 to Deininger discloses a method for
transuranic element polishing from radioactive wastewater using
FeO.sub.4.sup.2- that involves adjusting the pH of a transuranic
element-containing water source to a range of 6.5-14.0. Supposedly,
removal occurs by co-precipitation of the transuranics within the
ferric hydroxide matrix similar to other heavy metals. Also, small
amounts of a chemical are used compared to common technology. Based
on chemical dosages, radioactive sludge generation using this
method is reduced by 3-20%, depending on the suspended solids
content in the wastewater feed (Deininger, et al., Waste Manage.
'90, vol. 1, pp. 789-795 (1990)).
F. Use in Surface Cleaning
[0222] Dilute solutions of ferrate can be used for oxidizing
pretreatment of chromium (III) oxide containing films, resulting
from corrosion of base metal surfaces of piping systems and the
like, to render the corrosion films more amenable to conventional
chemical cleaning treatments. There is an existing need for
replacement of currently used laboratory oxidants, especially the
chromate derivatives. Chromate and chlorine are of environmental
concern, and in chromate oxidations, Cr(III) is formed, which is a
suspected carcinogen. Also, in permanganate reactions, MnO.sub.2 is
generated.
[0223] Removal of heavy metals, such as Cu, Cd, and Mn using
ferrate is also known. Ferrate has been shown to remove colloidal
suspensions and heavy metals through flocculation (T. Suzuki, Odaku
Kenkyu, Vol. 11 (5), p. 293-296 (1988)). The mechanism for Mn
removal involves the oxidative formation of insoluble MnO.sub.2 and
subsequent entrapment of these metals into the Fe(OH).sub.3
precipitate resulting from ferrate's reduction product. Cu and Cd
are removed in a similar manner. The removal of heavy metal ions
and humic acid by coagulation after treatment with potassium
ferrate has been studied. Metal ions are generally trapped during
sedimentation (F. Kazama and K. Kato, Kogyo Yosui, Vol. 357, p.
8-13 (Chemical Abstract 110:63421y) (1988)).
[0224] Additionally, metallic surfaces, such as those used in
medical devices or in the semi-conductor industry, need to be
cleaned or disinfected. Current methods for cleaning metal surfaces
require their exposure to disinfectants, such as bleach, that are
highly corrosive. Consequently, the metal parts corrode and
routinely fail due to fatigue and need to be replaced. Aside from
the high cost of replacing the corroded metal pieces, the failure
of the instruments create discomfort and annoyance for the users
and liabilities for the manufacturers.
[0225] Ferrate produced by the methods of the present invention can
be used to clean the surfaces of these metal parts. Ferrate is not
corrosive and does not damage the integrity of the metal piece. As
mentioned above, the biocidal activity of ferrate is comparable to
that of bleach. Therefore, ferrate provides an efficient,
effective, and economical means by which these metal surfaces can
be cleaned.
G. Medical Uses
[0226] In the medical arts, there is a great need to disinfect and
clean instruments and surfaces. The ferrate generating device of
the present invention can be used in a hospital setting for such a
use.
[0227] In certain other embodiments, the ferrate generated by the
methods of the present invention may be used to treat a wound, as
described in U.S. Pat. No. 6,187,347, which is incorporated herein
by reference in its entirety.
H. Use in Treating Bilge Water
[0228] The ferrate generated according to the present invention may
be used to treat bilge water.
[0229] The restoration and maintenance of the chemical, physical
and biological integrity of navigable water ways, including rivers,
streams, lakes and oceans are increasingly receiving greater
attention. Legislation has been enacted and regulations promulgated
requiring certain procedures and establishing standards for
restoring and maintaining the chemical, physical and biological
integrity of navigable waters, including rivers, streams, lakes and
oceans. One regulation governs the discharge of oil and other
hazardous substances into navigable waters. Boaters and marine
maintenance services are subject to such regulations due to the
potential for the discharge of hazardous substances from boats, and
particularly due to the potential for the discharge of contaminated
bilge water.
[0230] It is periodically necessary to clean the bilge of a vessel
due to the collection of stagnant, fouled, contaminated or
otherwise dirty water. This stagnant, fouled, contaminated or
otherwise dirty water typically includes oil, gasoline and/or
diesel fuel which can create hazardous conditions and be
particularly difficult to remove from the bilge. Certain laws and
regulations prohibit may "discharge," which includes any spiking,
spilling, leaking, or dumping of any kind of oil in any form
including fuel oil, gasoline, lubricating oil and oil mixed with
water in a vessel's bilge. Bilge water must be periodically pumped
from the bilge of a boat. Bilge water may be fouled by a wide
variety of contaminants, including motor oils, transmission, power
steering and hydraulic trim fluids, fuel from the engine (gas or
diesel), and solvents and paints used during repair and cleaning.
Furthermore, bilge water may be contaminated with bacteria, flora,
and/or fauna incompatible with the waters into which is intended to
be discharged.
[0231] For this reason, bilge water is commonly cleaned or
otherwise decontaminated and then the treated bilge water is
removed from the bilge at a discharge station. Liquid cleaners may
be used, added to the bilge water and after a short period of time,
the boat is taken to a discharge station and the treated bilge
water is pumped out. Such liquid cleaners do not satisfactorily
break down the oil or the other organic materials and often leave
an oil film in the bilge. If the liquid cleaner leaves a residue of
oil, gasoline or the like, the residue contributes to the
conditions which will require a subsequent cleaning and may enhance
corrosion of the materials used in manufacturing the vessel.
Furthermore, certain known liquid cleaners are non-biodegradable
and may further contribute to the pollution problem. Thus, although
there do exist systems for the filtrations and/or decontamination
of bilge water, such in-line systems, capable of automatically
cleaning and/or decontaminating bilge water prior to its discharge
overboard are not sufficient to meet current needs, extremely
complicated, cost prohibitive, or not widely accepted by either
industry or relevant regulatory authorities.
[0232] The disclosed method may be used to generate ferrate for the
cost-effective on-site treatment of bilge water, and the disclosed
device may be readily fitted such that, for example, the ferrate
produced according to the methods or by the device disclosed herein
is mixed with the bilge water in a mixing chamber, whereby oil
and/or organic contaminants are oxidized to innocuous products, the
iron salts are filtered away, and the clean bilge water is then
dispensed. This represents a highly effective and cost-efficient
method of decontaminating bilge water; ferrate produced by the
present methods is less costly than purchasing numerous oxidants
and other known methods of treating bilge water.
I. Ballast Water Treatment Using Ferrate
[0233] The introduction of non-indigenous species into marine
ecosystems by the shipping industry is an ever-increasing problem.
Contamination is caused by species carried on ship hulls and in
ballast water into new marine environments. Ship hull contamination
has been minimized through the use of antifoulants; however
transport of potentially harmful phytoplankton, microorganisms,
viruses, and invertebrates in ballast water and sediments threatens
marine environments throughout the world. Documentation of the
introduction of aquatic nuisance species (ANS) and harmful
consequences are reported in the literature and range from
paralytic shellfish poisoning by dinoflagellates to European zebra
mussel infestation in the Great Lakes. The resulting ecosystem
impacts and environmental degradation have severe economic
implications.
[0234] Ballast water is used to stabilize ships as cargo is loaded
and unloaded. The volume of shipboard ballast water ranges from
less than 100,000 to 14 million gallons (USEPA, 2001) or
approximately 400 to 56,000 m.sup.3. It is estimated that over 21
billion gallons of ballast water are discharged into US waters each
year, containing as many as 10,000 marine specimens. Historically,
the best practice for control of ANS has been mid-ocean exchange,
which has limited effectiveness due to incomplete water removal.
Some studies put the organism removal efficiency by mid-ocean
exchange as low as 25% (USEPA, 2001). In addition, mid-ocean
exchange can be dangerous, particularly in storm conditions, some
ships are not structurally designed for ballast water exchange, it
is not applicable to lake shipping, and it is difficult to verify
effectiveness. A National Research Council Report and the Global
Pollution Water Management Program both identify shipboard
treatment processes as the most desirable approach to managing ANS
(NRC, 1996; Globallast, Global Ballast Water Management Program,
1.sup.st International Ballast Water Treatment Standards Workshop
Report, IMO, London, March 2001.). These treatment processes
include physical separation, ultraviolet (UV) treatment, chemical
biocides, heating, ultrasound, magnetic fields and a combination of
these processes. A brief description of the more established
technologies including physical separation, UV treatment, and
biocides is provided below.
[0235] Ballast Water Treatment Options.
[0236] Proven physical ballast water treatment processes include
cyclonic separation and filtration. Cyclonic separation has been
shown to be quite effective at removing larger particles and biota
(Glosten-Herber-Hyde Marine, "Full-Scale Design Studies of Ballast
Water Treatment Systems," Prepared for the Great Lakes Ballast
Technology Demonstration Project, Northeast-Midwest Institute,
Washington, D.C., April 2002; Sutherland, T. F. C. D. Levings, C.
C. Elliott, W. W. Hesse 2001. Effect of a ballast water treatment
system on Survirvorship of natural populations of marine plankton.
(Marine Ecology Progress Series, 210:139-148 (2001)). Centrifugal
force is applied as water is forced through a vortex at high
velocity. Larger material is pushed to the periphery of the
spinning fluid and ejected in a reject stream (approximately 5-10%
of the total flow) and discharged overboard. Advantages of this
treatment process are that it involves proven technology, can be
retrofitted into a ship, can be automated, and has low pumping
requirements. However, it does not completely remove turbidity,
which may impact downstream processes; has almost no removal
capability for microorganisms, viruses, and phytoplankton; and is
expensive to install.
[0237] Filtration units are frequently used for water treatment and
can be designed to remove particulate matter as small as 0.01
.mu.m. However, filters capable of removing these small materials
are extremely expensive and cannot handle large flows typical of
many ships. Units capable of removing particles greater than 50
.mu.m are more applicable to shipboard operations; however, while
they would effectively remove zooplankton and some phytoplankton,
they will not remove microorganisms. Filter units can be automated,
but the process of backwashing to remove entrained material
adversely impacts ballast water pumping.
[0238] Ultraviolet treatment of ballast water has been evaluated at
laboratory and pilot-scale (Sutherland et al, 2001 and Waite T. D.
et al. "Removal of natural populations of marine plankton by a
large-scale ballast water treatment system" Marine Ecology Progress
Series, 258:51-63 (2003)). Again this treatment process has a
proven history in standard water and wastewater applications. In
laboratory studies UV treatment of cyclone treated ballast water
was found to be more effective in removing bacteria and viruses
than zooplankton and phytoplankton. Evidence of DNA repair during
storage was observed for some phytoplankton, resulting in regrowth.
Cyclone pretreatment was necessary to reduce turbidity that might
otherwise interfere with UV effectiveness.
[0239] Various chemical biocides have been utilized including
chlorine, glutaraldehye, SeaKleen, and acrolein (USEPA, 2001).
These chemicals can be injected into ballast fill or discharge
lines, thus requiring minor retrofitting of equipment. However,
while these biocides are quite effective at controlling
microorganisms and small zooplankton, sizeable doses are required
to kill larger aquatic species resulting in high costs and
potentially excessive residuals. Discharging of ballast water
containing residual biocides is problematic. Physical separation is
therefore necessary as a first stage treatment to reduce chemical
dosage requirements.
[0240] In all cases, cost estimates suggest that shipboard
treatment using current technology is orders of magnitude more
expensive than mid-ocean exchange. The identification of a low-cost
and highly-effective treatment approach is mandatory to prevent the
spread of ANS that will have a regulatory and economic impact on
worldwide shipping.
[0241] Full-Scale Implementation.
[0242] The Globallast Workshop (Globallast, 2001) has identified
minimum design requirements for implementing shipboard ballast
water treatment facilities. These include (1) minimal environmental
impact, (2) effective in destroying target biological species, (3)
safe for both the crew and the facilities, (4) compatible with ship
needs and requirements, and (5) cost effectiveness. In addition
other implementation considerations include the following: (1)
treatment on intake or discharge, (2) regrowth potential (if the
removal is less than 100%), (3) cross contamination from piping
and/or tanks, (4) effects of vibration and ship movement, (5)
corrosion due to salt water environment, and (6) the need for
automation and minimal operator attention (Glosten-Herber-Hyde
Marine, 2002). Any assessment of a ballast water treatment approach
must include consideration for these requirements.
[0243] Ferrate (VI)--An Environmentally Friendly Solution.
[0244] Iron in +6 oxidation state, (ferrate), can meet these
requirements economically due to its strength as an oxidant,
disinfectant, and coagulant all delivered in one treatment
chemical. Most importantly, its treatment by-product is non-toxic
Fe(III).
[0245] Treatment of ballast water by Fe(VI) does not result in any
mutagenic/carcinogenic by-products, which make ferrate an
environmentally-friendly solution. Moreover, the ferric oxide
produced from Fe(VI), acts as a powerful coagulant that is suitable
for the removal of metals, non-metals, and humic acids (Qu, J-H,
H-J. Liu, S-X. Liu, P. J. Lei. 2003 Reduction of fulvic acid in
drinking water by ferrate. J. Environ. Engg. 129: 17-24).
[0246] Fe(VI) shows excellent disinfectant properties and can
eliminate a wide variety of microorganisms at very low ferrate
doses. In contrast to UV technology, ferrate inactivation to
microorganisms is irreversible. Ferrate can interfere with both
polymerase and nuclease activities and to degrade
deoxyribonucleosides (Reddy, G. V. B. Nanduri, A. Basu, M. J.
Modal. 1991 Ferrate oxidation of murine leukemiavirus reverse
transcriptase: identification of the template-primer binding
domain. Biochemistry 30: 8195-8201; Stevenson C. J. H. Davies. 1995
Potassium ferrate as DNA sequencing reagent and probe of secondary
structure. Biochem. Soc. Trans. 23: 387S). This mechanism is
responsible for unique disinfection capability of ferrate.
[0247] Removal of total and fecal coliform by ferrate in wastewater
has been tested (Kazama, F. 1995 Viral inactivation by potassium
ferrate. Water Sci. Technol. 31: 165-168; Kazama, F. 1994
Inactivation of coliphage Q.beta. by potassium ferrate. J. Ferment.
Bioeng. 67: 369-373; Jiang et al. 2002). Ferrate treatment of water
sources collected worldwide has achieved complete removal of total
coliforms. Chlorine resistant bacteria can be easily treated with
ferrate. For example, an aerobic spore-formers can be reduced up to
3-log units while sulfite-reducing clostridia are effectively
killed by Fe(VI). Fe(VI) also rapidly inactivates virus f2 at low
concentrations in water (Schink, T. T. D. Waite 1980 Inactivation
of f2 virus with ferrate(VI). Water Research 14: 1705-1717).
Ferrate treatment removed algae in water in conjunction with alum
(Ma, J. W. Liu. 2002 Effectiveness and mechanism of potassium
ferrate(VI) preoxidation for algae removal by coagulation. Water
Research 36: 871-878).
[0248] We have conducted preliminary ferrate disinfection tests of
harbor waters at two locations in the Port of Cape Canaveral, Fla.
Sample A was collected at the inner Port, while Sample B was
collected closer to the exit at the Port nearer to the open ocean.
The results for Total Coliform, E. coli, and Heterotrophic
bacterial plate counts are summarized in the table below:
TABLE-US-00001 Total Coliform E. Coli HPC Ferrate dose MPN/100 mL
MPN/100 mL cfu/mL FeO.sub.4.sup.2-, mg/L A B A B A B 0.0 341 122 82
5 365 710 0.5 <1 <1 <1 <1 N/A N/A 1.0 <1 <1 <1
<1 N/A N/A 2.0 <1 <1 <1 <1 <5 <5
[0249] The total coliform in Sample A was reduced to non-detectable
levels with the addition of a very small ferrate dose of only 0.5
mg/L. Ferrate disinfection for Eschericha coli (E. coli) in both
samples was also examined. Again, ferrate was effective in killing
E. coli at a very low dose (0.5 mg/L). The levels of Heterotrophic
bacteria in both samples A and B were also reduced to
non-detectable values by ferrate at a dose of approximately 2 mg/L.
The results in Table 1 clearly demonstrate the ferrate's potential
for treating bacterial species in ballast water.
[0250] Thus, in another aspect, the present invention relates to a
method of treating ballast water, comprising: [0251] a) mixing an
iron salt and an oxidizing agent in a mixing chamber to provide a
mixture; [0252] b) delivering at least a portion of the mixture to
a reaction chamber; [0253] c) continuously generating ferrate in
the reaction chamber; [0254] d) delivering at least a portion of
the ferrate to a site of use that is proximal to the reaction
chamber, wherein said site of use is a site where said ballast
water is held; [0255] e) contacting said ferrate with said ballast
water, whereby organic matter in said ballast water is oxidized;
and [0256] f) adding additional iron salt and oxidizing agent to
the mixing chamber.
[0257] By "ballast water" it is meant any volume of water that is
used in a ship or other floatable device, such as a cargo
container, a barge, a submarine, and the like, in order to
stabilize the ship or the floatable device and prevent the ship or
the floatable device from capsizing when cargo or additional weight
is added or removed from the ship or the floatable device.
[0258] The ballast water may be held in the cargo-hold of the ship
or the floatable device, or in any other chamber within the ship or
the floatable device. In some embodiments, ferrate is added to the
ballast water as the ballast water is held within the chamber. In
other embodiments, ferrate is added to the ballast water as the
ballast water is being pumped, or otherwise introduced, into the
chamber. In yet other embodiments, ferrate is added to the ballast
water as the ballast water is being pumped out of, or otherwise
removed from, the chamber. In other embodiments, the ballast water
is mixed with ferrate prior to being pumped into the ship or the
floatable device.
[0259] In some embodiments, the device for generating ferrate is
located on the ship, or nearby, whereby the output valve for the
device is connected to the location of ballast water by a hose or a
pipe, so that ferrate is directly injected into the ballast water.
In other embodiments, the ferrate is generated at a site proximal
to the site where the ballast water is located, and the ferrate is
taken there in a vessel, such as a tank, drums, buckets, etc.
[0260] As disclosed herein, ballast water comprises organic matter,
such as marine plants, animals, algae, bacteria, ameba, viruses,
etc. Ferrate, as a strong oxidant, is capable of oxidizing the
organic matter, and thereby killing some, or all, of the living
organisms within the ballast water, and/or render some or all of
the organic matter biologically inactive. In some embodiments, the
level of biologically active organic matter in ballast water is
reduced to a level at or below a level set forth by the proper
authority at a particular port city, state, or country.
[0261] In another aspect, the present invention relates to a method
of synthesizing ferrate, comprising: [0262] a) mixing an aqueous
solution comprising an iron salt and an oxidizing agent in a mixing
chamber to form a solution of ferrate; [0263] b) delivering at
least a portion of the solution of ferrate to a site of use that is
proximal to the mixing chamber, wherein said site of use is a site
where said ballast water is held; and [0264] c) contacting said
ferrate with said ballast water, whereby organic matter in said
ballast water is oxidized.
VI. SOME EMBODIMENTS OF THE INVENTION
[0265] Some of the embodiments of the invention refer to the
following:
[0266] A method of continuously synthesizing ferrate, comprising:
[0267] a) mixing an aqueous solution comprising an iron salt and an
oxidizing agent in a mixing chamber; [0268] b) delivering at least
a portion of the aqueous solution to a reaction chamber; [0269] c)
continuously generating ferrate in the reaction chamber; [0270] d)
delivering at least a portion of the ferrate to a site of use that
is proximal to the reaction chamber; and [0271] e) adding
additional aqueous solution to the mixing chamber.
[0272] The above method, where the additional aqueous solution in
step (e) is added in an amount to substantially replace the portion
of the aqueous solution delivered to the reaction chamber.
[0273] The above method, further comprising adding a base to the
aqueous solution.
[0274] The above method, where the base comprises an ion selected
from the group consisting of a nitrogen base, the hydroxide ion,
the oxide ion, and the carbonate ion, or a combination thereof.
[0275] The above method, where the iron salt is selected from the
group consisting of ferric nitrate, ferrous nitrate, ferric
chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric
sulfate, ferrous sulfate, ferric phosphate, ferrous phosphate,
ferric hydroxide, ferrous hydroxide, ferric oxide, ferrous oxide,
ferric hydrogen carbonate, ferrous hydrogen carbonate, ferric
carbonate, and ferrous carbonate, or a combination thereof.
[0276] The above method, where the oxidizing agent comprises at
least one of the following: a hypohalite ion, a halite ion, a
halate ion, a perhalate ion, ozone, oxone, halogen, a peroxide, a
peracid, a salt of a peracid, and Caro's acid, or a combination
thereof.
[0277] The above method, where the oxidizing agent comprises a
hypohalite ion selected from the group consisting of the
hypochlorite ion, the hypobromite ion, and the hypoiodite ion.
[0278] The above method, where the oxidizing agent comprises a
halite ion selected from the group consisting of the chlorite ion,
the bromite ion, and the iodite ion.
[0279] The above method, where the oxidizing agent comprises a
halate ion selected from the group consisting of the chlorate ion,
the bromate ion, and the iodate ion.
[0280] The above method, where the oxidizing agent comprises a
perhalate ion selected from the group consisting of the perchlorate
ion, the perbromate ion, and the periodate ion.
[0281] The above method, additionally comprising repeating steps
(b) through (d).
[0282] A method of treating, at a site of use, an aqueous mixture
having at least one impurity, comprising [0283] a) continuously
generating ferrate in a reaction chamber located proximal to the
site of use; [0284] b) contacting the ferrate with the aqueous
mixture at the site of use, whereby at least a portion of the
impurity is oxidized.
[0285] The above method, where the impurity is selected from the
group consisting of a biological impurity, an organic impurity, an
inorganic impurity, a sulfur-containing impurity, a metallic
impurity, and a radioactive impurity, or a combination thereof.
[0286] The above method, where the step of continuously generating
ferrate comprises the steps of: [0287] a) mixing an aqueous
solution comprising an iron salt and an oxidizing agent in a mixing
chamber; [0288] b) delivering at least a portion of the aqueous
solution to a reaction chamber; [0289] c) continuously generating
ferrate in the reaction chamber; [0290] d) delivering at least a
portion of the ferrate to a site of use that is proximal to the
reaction chamber; and [0291] e) adding additional aqueous solution
to the mixing chamber.
[0292] The above method, where the additional aqueous solution
added in step (e) is in an amount to substantially replace the
portion of the aqueous solution delivered to the reaction
chamber.
[0293] The above method, further comprising adding a base to the
aqueous solution.
[0294] The above method, where the base comprises an ion selected
from the group consisting of the hydroxide ion, the oxide ion, and
the carbonate ion, or a combination thereof.
[0295] The above method, where the iron salt is selected from the
group consisting of ferric nitrate, ferrous nitrate, ferric
chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric
sulfate, ferrous sulfate, ferric phosphate, ferrous phosphate,
ferric hydroxide, ferrous hydroxide, ferric oxide, ferrous oxide,
ferric hydrogen carbonate, ferrous hydrogen carbonate, ferric
carbonate, and ferrous carbonate, or a combination thereof.
[0296] The above method, where the oxidizing agent comprises a
component selected from the group consisting of a hypohalite ion, a
halite ion, a halate ion, a perhalate ion, ozone, oxone, halogen, a
peroxide, a peracid, a salt of a peracid, and Caro's acid, or a
combination thereof.
[0297] The above method, where the oxidizing agent comprises a
hypohalite ion selected from the group consisting of the
hypochlorite ion, the hypobromite ion, and the hypoiodite ion.
[0298] The above method, where the oxidizing agent comprises a
halite ion selected from the group consisting of the chlorite ion,
the bromite ion, and the iodite ion.
[0299] The above method, where the oxidizing agent comprises a
halate ion selected from the group consisting of the chlorate ion,
the bromate ion, and the iodate ion.
[0300] The above method, where the oxidizing agent comprises a
perhalate ion selected from the group consisting of the perchlorate
ion, the perbromate ion, and the periodate ion.
[0301] The above method, where the contacting step comprises adding
the ferrate to a stream of the aqueous mixture.
[0302] The above method, where the contacting step comprises
contacting the ferrate to a pool of the aqueous mixture.
[0303] The above method, where the contacting step comprises
contacting a stream of the aqueous mixture with a stationary
container containing the ferrate.
[0304] The above method, additionally comprising repeating steps
(b) through (d).
[0305] A device for continuously synthesizing ferrate for delivery
to a site of use, comprising: [0306] a) a first holding chamber;
[0307] b) a second holding chamber; [0308] c) a mixing chamber
controllably connected to the first holding chamber and to the
second holding chamber, into which a content of the first holding
chamber and a content of a second holding chamber are added to form
a first mixture; [0309] d) a reaction chamber controllably
connected to the mixing chamber, the reaction chamber adapted to
receive the first mixture and maintain the first mixture for a
period of time; [0310] e) a ferrate mixture in the reaction
chamber; and [0311] f) an output opening in the reaction chamber
through which the ferrate mixture is adapted to be transported to
the site of use, where the site of use is proximal to the reaction
chamber.
[0312] The above device, where the mixing chamber further comprises
a mechanical agitator.
[0313] The above device, where the mixing chamber comprises a tube
configured to mix the mixture as it passes through the tube.
[0314] The above device, where the mixing chamber further comprises
a temperature control device.
[0315] The above device, further comprising a pump downstream from
the first and the second holding chambers and upstream from the
mixing chamber.
[0316] The above device, further comprising a pump downstream from
the mixing chamber and upstream from the reaction chamber.
[0317] The above device, where the reaction chamber comprises a
tube located between the mixing chamber and the output opening.
[0318] A system for continuously synthesizing ferrate, comprising:
[0319] a) a first holding chamber containing an iron salt; [0320]
b) a second holding chamber containing an oxidizing agent; [0321]
c) a mixing chamber controllably connected to the first holding
chamber and to the second holding chamber, into which the iron salt
and the oxidizing agent are controllably added to form a mixture;
[0322] d) a reaction chamber controllably connected to the mixing
chamber, into which the mixture is kept for a period of time, and
in which ferrate is synthesized, and [0323] e) an output opening in
the reaction chamber through which the ferrate is adapted to be
transported to a proximal site of use.
[0324] The above system, further comprising adding a base to the
mixture.
[0325] The above system, where the base comprises an ion selected
from the group consisting of the hydroxide ion, the oxide ion, and
the carbonate ion, or a combination thereof.
[0326] The above system, where the iron salt is selected from the
group consisting of ferric nitrate, ferrous nitrate, ferric
chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric
sulfate, ferrous sulfate, ferric phosphate, ferrous phosphate,
ferric hydroxide, ferrous hydroxide, ferric oxide, ferrous oxide,
ferric hydrogen carbonate, ferrous hydrogen carbonate, ferric
carbonate, and ferrous carbonate, or a combination thereof.
[0327] The above system, where the oxidizing agent comprises a
component selected from the group consisting of a hypohalite ion, a
halite ion, a halate ion, a perhalate ion, ozone, oxone, halogen, a
peroxide, a peracid, a salt of a peracid, and Caro's acid, or a
combination thereof.
[0328] The above system, where the oxidizing agent comprises a
hypohalite ion selected from the group consisting of the
hypochlorite ion, the hypobromite ion, and the hypoiodite ion.
[0329] The above system, where the oxidizing agent comprises a
halite ion selected from the group consisting of the chlorite ion,
the bromite ion, and the iodite ion.
[0330] The above system, where the oxidizing agent comprises a
halate ion selected from the group consisting of the chlorate ion,
the bromate ion, and the iodate ion.
[0331] The above system, where the oxidizing agent comprises a
perhalate ion selected from the group consisting of the perchlorate
ion, the perbromate ion, and the periodate ion.
[0332] The above system, where the mixing chamber further comprises
a mechanical agitator.
[0333] The above system, where the mixing chamber comprises a tube
configured to mix the mixture as it passes through the tube.
[0334] The above system, where the mixing chamber further comprises
a temperature control device.
[0335] The above system, further comprising a pump downstream from
the first and the second holding chambers and upstream from the
mixing chamber.
[0336] The above system, further comprising a pump downstream from
the mixing chamber and upstream from the reaction chamber.
[0337] The above system, where the reaction chamber comprises a
tube located between the mixing chamber and the output opening.
[0338] A method of purifying drinking water comprising contacting
ferrate generated by the above methods with the drinking water,
where the contacting is at a site proximal to the generation
site.
[0339] A method of purifying waste water comprising contacting
ferrate generated by the above methods with the waste water, where
the contacting is at a site proximal to the generation site.
[0340] A method of purifying sewage comprising contacting ferrate
generated by the above methods with the sewage, where the
contacting is at a site proximal to the generation site.
[0341] A method of cleaning surgical instruments comprising
contacting ferrate generated by the above methods with the surgical
instruments, where the contacting is at a site proximal to the
generation site.
[0342] A method of removing radioactive materials from an aqueous
solution comprising contacting ferrate generated by the above
methods with the aqueous solution, where the contacting is at a
site proximal to the generation site.
[0343] A method of cleaning a metallic or a polymer surface
comprising contacting ferrate generated by the above methods with
the metallic or a polymer surface, where the contacting is at a
site proximal to the generation site.
[0344] A method of coating a metallic or a polymer surface
comprising contacting ferrate generated by the above methods with
the metallic or a polymer surface, where the contacting is at a
site proximal to the generation site.
[0345] A method of continuously synthesizing ferrate, comprising:
[0346] a) providing a mixture of an iron salt and an oxidizing
agent; [0347] b) continuously delivering at least a portion of the
mixture to a heating chamber; [0348] c) exposing the mixture to
elevated temperatures in the heating chamber, thereby generating
ferrate; [0349] d) removing at least a portion of the ferrate
generated in step c) from the heating chamber; [0350] e) adding
additional mixture to the heating chamber.
[0351] The above method, where the additional mixture added to the
heating chamber is in an amount to substantially replace the
portion of the ferrate removed from the heating chamber.
[0352] The above method, further comprising adding a base to the
mixture.
[0353] The above method, where the base comprises an ion selected
from the group consisting of a nitrogen base, the hydroxide ion,
the oxide ion, and the carbonate ion, or a combination thereof.
[0354] The above method, where the iron salt is selected from the
group consisting of ferric nitrate, ferrous nitrate, ferric
chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric
sulfate, ferrous sulfate, ferric phosphate, ferrous phosphate,
ferric hydroxide, ferrous hydroxide, ferric oxide, ferrous oxide,
ferric hydrogen carbonate, ferrous hydrogen carbonate, ferric
carbonate, and ferrous carbonate, or a combination thereof.
[0355] The above method, where the oxidizing agent comprises a
component selected from the group consisting of a hypohalite ion, a
halite ion, a halate ion, a perhalate ion, halogen, a peroxide, a
peracid, a salt of a peracid, and Caro's acid, or a combination
thereof.
[0356] The above method, where the oxidizing agent comprises a
hypohalite ion selected from the group consisting of the
hypochlorite ion, the hypobromite ion, and the hypoiodite ion.
[0357] The above method, where the oxidizing agent comprises a
halite ion selected from the group consisting of the chlorite ion,
the bromite ion, and the iodite ion.
[0358] The above method, where the oxidizing agent comprises a
halate ion selected from the group consisting of the chlorate ion,
the bromate ion, and the iodate ion.
[0359] The above method, where the oxidizing agent comprises a
perhalate ion selected from the group consisting of the perchlorate
ion, the perbromate ion, and the periodate ion.
[0360] The above method, where the mixture exposed to elevated
temperature is a solid.
[0361] A device for continuously synthesizing ferrate, comprising:
[0362] a) a holding chamber; [0363] b) a mover controllably
connected to the holding chamber such that at least a portion of a
content of the holding chamber is transferred to the mover; [0364]
c) a heating chamber, through which at least a portion of the mover
moves; [0365] d) an output opening in the heating chamber through
which the content on the mover is adapted to be transported to a
site of use,
[0366] where the site of use is proximal to the heating
chamber.
[0367] The above device, where the mover comprises a conveyor
belt.
[0368] The above device, further comprising a mixer between the
holding chamber and the mover.
[0369] The above device, where the heating chamber further
comprises a temperature control device.
[0370] The above device, further comprising a storage chamber after
the output opening in the heating chamber.
[0371] A device for continuously synthesizing ferrate, comprising:
[0372] a) a reaction chamber comprising two electrodes and a
solution of an iron salt, where the electrodes provide sufficient
electric current to convert the solution of an iron salt to a
solution of ferrate; [0373] b) a holding chamber controllably
connected to the reaction chamber, into which the solution of
ferrate is kept for a period of time; and [0374] c) an output
opening in the holding chamber through which the mixture is adapted
to be transported to a site of use,
[0375] where the site of use is proximal to the holding
chamber.
[0376] The above device, where the reaction chamber further
comprises a mechanical agitator.
[0377] The above device, where the reaction chamber comprises a
tube configured to mix the mixture as it passes through the
tube.
[0378] The above device, where the reaction chamber further
comprises a temperature control device.
[0379] The above device, further comprising a pump downstream from
the first and the second holding chambers and upstream from the
reaction chamber.
[0380] The above device, further comprising a pump downstream from
the reaction chamber and upstream from the holding chamber.
[0381] The above device, where the holding chamber comprises a tube
located between the reaction chamber and the output opening.
[0382] A method of continuously synthesizing ferrate, comprising:
[0383] a) continuously providing an aqueous solution comprising an
iron salt in a reaction chamber, where the reaction chamber
comprises at least two electrodes; [0384] b) providing sufficient
electric current to the at least two electrodes to convert at least
a portion of the iron salt to ferrate; [0385] c) delivering at
least a portion of the ferrate to a site of use that is proximal to
the reaction chamber; and [0386] d) adding additional aqueous
solution to the reaction chamber.
[0387] The above method, where the additional aqueous solution
added in step (d) is in an amount sufficient to substantially
replace the portion of the aqueous solution delivered to the
reaction chamber.
[0388] The above method, further comprising adding a base to the
aqueous solution.
[0389] The above method, further comprising adding an acid to the
aqueous solution.
[0390] The above method, where the iron salt is selected from the
group consisting of ferric nitrate, ferrous nitrate, ferric
chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric
sulfate, ferrous sulfate, ferric phosphate, ferrous phosphate,
ferric hydroxide, ferrous hydroxide, ferric oxide, ferrous oxide,
ferric hydrogen carbonate, ferrous hydrogen carbonate, ferric
carbonate, and ferrous carbonate, or a combination thereof.
[0391] A method of synthesizing ferrate, comprising: [0392] a)
mixing an aqueous solution comprising an iron salt and an oxidizing
agent in a mixing chamber to form a solution of ferrate; [0393] b)
delivering at least a portion of the solution of ferrate to a site
of use that is proximal to the mixing chamber.
[0394] The above method, further comprising adding a base to the
aqueous solution.
[0395] The above method, where the base comprises an ion selected
from the group consisting of a nitrogen base, the hydroxide ion,
the oxide ion, and the carbonate ion, or a combination thereof.
[0396] The above method, where the iron salt is selected from the
group consisting of ferric nitrate, ferrous nitrate, ferric
chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric
sulfate, ferrous sulfate, ferric phosphate, ferrous phosphate,
ferric hydroxide, ferrous hydroxide, ferric oxide, ferrous oxide,
ferric hydrogen carbonate, ferrous hydrogen carbonate, ferric
carbonate, and ferrous carbonate, or a combination thereof.
[0397] The above method, where the oxidizing agent comprises a
component selected from the group consisting of a hypohalite ion, a
halite ion, a halate ion, a perhalate ion, ozone, oxone, halogen, a
peroxide, a peracid, a salt of a peracid, and Caro's acid, or a
combination thereof.
[0398] The above method, where the oxidizing agent comprises a
hypohalite ion selected from the group consisting of the
hypochlorite ion, the hypobromite ion, and the hypoiodite ion.
[0399] The above method, where the oxidizing agent comprises a
halite ion selected from the group consisting of the chlorite ion,
the bromite ion, and the iodite ion.
[0400] The above method, where the oxidizing agent comprises a
halate ion selected from the group consisting of the chlorate ion,
the bromate ion, and the iodate ion.
[0401] The above method, where the oxidizing agent comprises a
perhalate ion selected from the group consisting of the perchlorate
ion, the perbromate ion, and the periodate ion.
[0402] A method of treating, at a site of use, an aqueous mixture
having at least one impurity, comprising [0403] a) continuously
generating ferrate in a reaction chamber located proximal to the
site of use; [0404] b) contacting the ferrate with the aqueous
mixture at the site of use, whereby at least a portion of the
impurity is coagulated.
EXAMPLES
Example 1: Preparation of Ferrate(VI)
[0405] The following is one representative embodiment of a
laboratory procedure for synthesizing ferrate. Add 75 mL distilled
water to a 250 mL beaker. Add 30 g of NaOH to result in a 10 M
solution. Cool the caustic solution in an ice bath. Pump
Cl.sub.2(g) (approximately 6.5 g) into the solution while mixing.
Add a second batch (70 g) of NaOH to the hypochlorite solution.
Keep the solution cool. Coarse filter the precipitated salt
residue. Add 25 g of Fe(NO.sub.3).sub.3.9H.sub.2O while stirring.
Filter through medium coarse filter. Analyze the Fe.sup.6+ yield
using UV-Vis spectroscopy by observing absorbance at about 510
nm.
Example 2: Synthesis and Measurement of Ferrate
[0406] Ferrate is synthesized using the procedure of Example 1,
except 16.35 g of chlorine was used instead of 6.5 g, and 25 g NaOH
is used as the second caustic addition instead of 70 g. 40 g of
coarse-glass-frit-filtered caustic/hypochlorite solution is added
to a 50 mL jacketed reaction vessel containing a TEFLON.RTM.-coated
magnetic stirring bar. Controlled temperature water is circulated
through the jacket to control and establish the reaction
temperature. 5.0 g of ferric nitrate nonahydrate
(Fe(NO.sub.3).sub.3.9H.sub.2O) is added over a period of a few
minutes to begin the experiment.
Temperature is set at 30.degree. C.
TABLE-US-00002 [0407] Time, Actual Expected Observed Fraction of
Iron Actual Reaction min Wt*, (g) Absorbance.dagger. Absorbance in
(VI) State Temperature, .degree. C. Notes 0 22.4 Begin iron
addition 2 27 Complete iron addition 2.5 30 3.5 33.9 Beginning of
reaction noted 5 0.33 1.04 0.25 0.24 31.1 10 0.32 1.01 0.40 0.40
30.7 17 0.31 0.98 0.48 0.49 30.4 25 0.33 1.04 0.59 0.57 30.4 35
0.32 1.01 0.60 0.59 30.3 45 0.34 1.08 0.695 0.64 30.5 *Actual Wt:
For the spectrophotometric analysis, an aliquot of the reaction
solution is taken gravimetrically and diluted with pH 10 buffer.
This is the weight of the aliquot. The dilution is to 100 g. The pH
10 buffer solution is prepared by combining 10.0 g sodium
phosphate, dibasic and 0.71 g of a 40 g/L sodium borate solution
with enough distilled water to make one liter of buffer solution.
.dagger.Expected Absorbance: "Expected Absorbance" refers to the
theoretical absorbance of the solution if all of the iron in the
solution had been converted to Fe(VI). The weight of the aliquot
represents a fraction of the total amount of iron in the
experiment. If all of this iron is present as ferrate, this is the
computed absorbance value of the solution. In combination with the
observed absorbance, the computed result facilitates determination
of the fraction of iron in the +6 state.
[0408] The concentration of Fe(VI) is measured by the absorbance
(A) of a buffered sample of the reaction product solution, relative
to the blank pH 10 buffer solution, with a UV-Vis spectrophotometer
set at a wavelength of 510 nm. The formula for the fraction of iron
converted to Fe(VI) is as follows:
fraction converted = A .times. 100 .times. RSW .times. MWIS MAC
.times. 1000 .times. SW .times. wtISinR ##EQU00001##
where A=absorbance measurement RSW=the reaction solution weight
(total weight in grams) SW=the sample weight of the reaction
solution taken to combine with 49.7-49.85 g buffer solution (about
0.3-0.15 g, respectively) MWIS=molecular weight of the iron source
wtISinR=weight of iron source used in reaction (in grams)
100=volume of buffer solution in cc's 1000=volumetric conversion
factor for cc/L MAC=molar absorptivity coefficient, which is equal
to 1150/Mcm for Fe(VI) in the pH 10 buffer solution at 510 nm
A=MAC.times.p.times.c
[0409] p=path length of the absorbance cell (cm) c=concentration of
Fe(VI) in g-moles per liter
Temperature is set at 35.degree. C.
TABLE-US-00003 [0410] Time, Actual Expected Observed Fraction of
Iron Actual Reaction min Wt, gm Absorbance Absorbance in (VI) State
Temperature, .degree. C. Notes 0 24 Begin iron addition 2 28.6
Complete iron addition 2.5 32 3.5 37 Beginning of reaction noted 5
0.32 0.285 1.01 0.28 36 10 0.34 0.52 1.08 0.48 35.4 17 0.34 0.61
1.08 0.56 35.3 25 0.34 0.67 1.08 0.62 35.3 35 0.31 0.68 0.98 0.69
35.3 45 0.34 0.813 1.08 0.75 35.3 60 0.43 1.11 1.36 0.82 35.2
[0411] This example shows that, under the given conditions, maximum
conversion of Fe(III) and maximum yield of Fe(VI) requires at least
60 minutes of reaction time; and that Fe(VI) formation, in this
case, is enhanced at 35.degree. C. over that obtained at 30.degree.
C.
Example 3: Preparation of Ferrate(VI)
[0412] Ferrate is synthesized using the procedure of Example 1,
except 13 g of chlorine was used instead of 6.5 g, and 25 g NaOH is
used as the second caustic addition instead of 70 g. Reaction
vessel is a jacketed beaker maintained at 35.degree. C. Begin with
20 g of caustic/hypochlorite solution. Gradually add 1.6 g of
ferric nitrate nonahydrate crystals. This is a 5 fold
stoichiometric excess of hypochlorite over ferric(III). The maximum
temperature achieved during this step was 39.degree. C.
TABLE-US-00004 Actual Actual Fraction of reaction Time, weight,
Expected Actual Iron in the temperature, min gm absorbance
absorbance (VI) state .degree. C. 15 0.3233 1.36 0.86 0.63 35.2 30
0.3427 1.44 1.14 0.79 35.2 45 0.2984 1.26 1.10 0.87 35.2 60 0.3289
1.39 1.25 0.90 35.2
[0413] This example shows that, compared with Example 2, the Fe(VI)
yield is increased by using more excess hypochlorite and caustic
solution relative to the Fe(III) content of the reaction mixture.
In this example, the volume of pH 10 buffer solution used was 50 cc
instead of 100 cc.
Example 4: Ferrate (VI) Decay Rates
[0414] Ferrate (VI) is synthesized and measured according to the
procedures of Examples 1 and 2, except that the following reactant
quantities are used:
TABLE-US-00005 Experiment Fe(NO.sub.3).sub.3.cndot.9H.sub.2O (g)
NaOH (g) Cl.sub.2 (g) A 6.01 13.6 3.24 B 4.19 13.6 3.47 C 2.41 13.6
3.24
[0415] In each case, the jacketed reaction vessel temperature is
controlled at 35.degree. C. for about the first 2 hours and then
allowed to slowly cool to ambient conditions (about 23.degree.
C.
TABLE-US-00006 Reaction Time Fraction of Fe (min.) in (VI) State
Experiment A 0 0 15 0.40 30 0.44 45 0.44 60 0.42 120 0.37 180 0.34
240 0.29 300 0.27 360 0.25 390 0.22 1410 0.16 Experiment B 0 0 15
0.50 30 0.59 45 0.65 60 0.69 75 0.71 105 0.73 175 0.74 239 0.76 359
0.76 479 0.76 1395 0.58 1500 0.56 1745 0.49 2920 0.33 Experiment C
0 0 28 0.75 43 0.85 60 0.90 75 0.91 90 0.93 120 0.93 150 0.93 210
0.94 270 0.95 390 0.95 506 0.96 566 0.96 1466 0.92 1576 0.91 1816
0.89 2991 0.86
[0416] These experiments show that ferrate (VI) is not stable over
long time periods; however, the stability and the half-life for
decomposition improve with higher ferrate yields. These experiments
also exemplify the concept of generating ferrate at a site proximal
to the site of use such that the two sites are within a distance
that allows for the ferrate to travel the distance within a
half-life of its decomposition. In this example, the half-life of
the ferrate in Experiments A and B is approximately 400 min and
2250 min, respectively. The half-life of ferrate in Experiment C is
greater than 3000 min; however, the consumption of Cl.sub.2 and
NaOH per unit weight of Fe(VI) is significantly greater than that
for Experiments A or B.
Example 5: Synthesis of Ferrate (VI) with Commodity Feeds
[0417] In this example, ferrate (VI) is synthesized with readily
available commodity liquid bleach (13.4 wt % NaOCl), commodity
liquid caustic (50.5 wt % NaOH), and 50 wt % ferric chloride in
water solution. Initially 30.03 g of bleach solution is placed in a
beaker containing a TEFLON.RTM.-coated magnetic stirring bar and
the bleach beaker is cooled in an ice/water bath to about
15.degree. C. Then 37.06 g of caustic solution is slowly added to
the bleach with stirring such that the temperature is maintained at
about 15-20.degree. C. The bleach/caustic solution is then
transferred to a jacketed reaction vessel. Then 2.97 g of 50%
ferric chloride solution is injected into the bleach/caustic
solution with a syringe needle positioned below the liquid level of
the stirred bleach/caustic solution. The jacketed reaction vessel
control temperature is then set at 30.degree. C., and sample
aliquots (about 0.3 g) are taken about every 30 minutes for Fe(VI)
yield measurements according to the procedure described in Example
2. In this case, the yield of ferrate peaked out at 68%.
Example 6: Synthesis of Ferrate (VI) with Commodity Feeds
[0418] Ferrate (VI) is synthesized utilizing the same liquid feed
materials and methodology as those used in Example 5, except 55.59
g of caustic solution is used instead of 37.06 g. In this case, the
yield of ferrate (VI) peaked out at 81%.
Example 7: Preparation of Ferrate(VI)
[0419] Ferrate is synthesized using the procedure of Example 1,
except that 17 g of chlorine was used instead of 6.5 g. 40 grams of
coarse glass frit filtered solution of hypochlorite in saturated
sodium hydroxide solution is added to a 50 mL Pyrex beaker with a
TEFLON.RTM. stirring bar. The beaker is placed in a large
crystallizing dish on a magnetic stirrer plate. The crystallizing
dish has a water/ice mixture to maintain a temperature of
19-20.degree. C. Five grams of ferric nitrate nonahydrate is added
over a period of four minutes to begin the experiment. The iron
salt distributes through the mixture but there is no visually
apparent activity for a few minutes. The temperature of the
reaction mixture slowly rises. About 10 minutes after the start of
the iron addition, the mixture turns dark purple. Simultaneously,
the reaction temperature peaks at 31.degree. C. At this point, a
timer is started for the taking of samples for Ferrate(VI)
analysis. The water/ice bath maintains a constant temperature of
19-20.degree. C.
TABLE-US-00007 Actual Fraction of Reaction Time, Actual Expected
Observed Iron in Temperature, min Wt, g Absorbance Absorbance (VI)
State .degree. C. 2 0.30 0.95 0.37 0.39 29 6 0.39 1.24 0.66 0.53 26
10 0.31 0.98 0.55 0.56 23 15 0.32 1.02 0.64 0.63 22 25 0.30 0.95
0.64 0.67 -- 35 0.29 0.92 0.66 0.72 -- 45 0.33 1.05 0.76 0.72 -- 60
0.31 0.98 0.71 0.72 --
Example 8: Preparation of Ferrate(VI)
[0420] Ferrate is synthesized using the procedure of Example 1. 30
g of NaOH plus 75 g of water were mixed in the reaction chamber,
followed by the addition of 6.5 g of Cl.sub.2. Another 70 g of NaOH
is added. The solution phase of this is reacted with 25 grams of
ferric nitrate.
TABLE-US-00008 Caustic, Experiment Temp, .degree. C. 1st/2nd
Chlorine, g Iron Form C vs. B.dagger-dbl. Agitation 1 30 30/25 13
25/60 Fe/H.sub.2O C T fitting 2 30 30/10 13 25/60 Fe/H.sub.2O C T
fitting 3 30 30/0 10 25/60 Fe/H.sub.2O C T fitting 4 35 30/0 10
25/60 Fe/H.sub.2O C T fitting 5 40 30/0 10 25/60 Fe/H.sub.2O C T
fitting 6 35 15/0 7.5 25/60 Fe/H.sub.2O C T fitting 7 30 30/25 13
25/60 Fe/H.sub.2O B Blade 8 30 30/10 13 25/60 Fe/H.sub.2O B Blade 9
30 30/0 10 25/60 Fe/H.sub.2O B Blade 10 35 30/0 10 25/60
Fe/H.sub.2O B Blade 11 40 30/0 10 25/60 Fe/H.sub.2O B Blade 12 35
15/0 7.5 25/60 Fe/H.sub.2O B Blade 13 30 30/25 13 25/60 Fe/H.sub.2O
C Passive 14 30 30/10 13 25/60 Fe/H.sub.2O C Passive 15 30 30/0 10
25/60 Fe/H.sub.2O C Passive 16 35 30/0 10 25/60 Fe/H.sub.2O C
Passive 17 40 30/0 10 25/60 Fe/H.sub.2O C Passive 18 35 15/0 7.5
25/60 Fe/H.sub.2O C Passive 19 30 30/25 13 25/60 basepm* C Passive
20 30 30/10 13 25/60 basepm C Passive 21 30 30/0 10 25/60 basepm C
Passive 22 35 30/0 10 25/60 basepm C Passive 23 40 30/0 10 25/60
basepm C Passive 24 35 15/0 7.5 25/60 basepm C Passive 25 35 30/0
10 25/30 sol 1.dagger. C Passive 26 35 30/0 10 25/30 sol 2 C
Passive 27 35 30/0 10 25/30 sol 3 C Passive 28 35 30/0 10 25/30 sol
4 C Passive 29 35 30/0 10 25/30 sol 5 C Passive 30 35 30/0 10 25/30
sol 6 C Passive *Basepm means pre mix the iron solution with some
of the NaOH in a short loop before contacting the bleach.
.dagger.Sol 1, 2, 3, 4, 5 and 6 means small chelating molecule
which might be needed to stabilize the iron with respect to loss by
precipitation as insoluble iron oxide. This approach might also
make it possible to reduce the amount of water in the recipe, this
helps by concentrating all of the species to improve the kinetics.
This may also cut down on forms of iron which are hostile to either
ferrate(VI) or bleach or both. .dagger-dbl.C vs. B means continuous
vs. batch.
Example 9: Preparation of Ferrate(VI)
[0421] Ferrate is synthesized using the procedure of Example 1,
except 12.9 g of chlorine was used instead of 6.5 g and the second
addition of sodium hydroxide was 25 g instead of 70 g. Reaction
vessel is a 30 mL beaker in a 30.degree. C. water bath. Begin with
15 g of hypochlorite/sodium hydroxide solution. Over two minutes,
add a proportionate amount of ferric nitrate nonahydrate crystals
(4.8 g). Begin pumping bleach into the vessel at a rate of 1.2 g
per minute. Simultaneously, continuously feed iron crystals into
the vessel at a rate of 0.24 g per minute. Stop after 20 minutes,
this point in time becomes time=0 in the table below. During this
period the maximum temperature was 40.degree. C. but mostly a
temperature of close to 30.degree. C. was maintained. After the
additions were stopped samples were taken for spectrophotometric
analysis.
TABLE-US-00009 Actual Actual Fraction of reaction Time, weight,
Expected Actual Iron in the temperature, min gm absorbance
absorbance (VI) state .degree. C. 0 0.3267 2.93 1.121 0.38 30.1 10
0.3284 2.94 1.294 0.44 28.8 20 0.3550 3.18 1.466 0.46 28.2
Example 10: Literature Preparation of Ferrate(VI)
[0422] Ferrate was synthesized using a recipe given by Audette and
Quail, Inorganic Chemistry 11(8) 1904 (1972).
TABLE-US-00010 IC 11(8) 1904 (1972) Experimental Procedure Weight,
grams Recipe Experi- On a 75 Weight, mental grams of Ingredient
grams Moles Moles Procedure water basis Water 75 10 75 1st NaOH 30
0.10 4 30 Cl.sub.2 (gas) 6.5 0.092 0.038 2.7 20.25 0.29 (75 g water
basis) 2nd NaOH 70 0.24 9.6 72 Ferric 25 0.062 0.005 2.02 15
Nitrate Nonahydrate
Example 11: Procedure for the Synthesis of Ferrate (VI)
[0423] Take a small sample bottle and record its tare weight to the
nearest 0.01 grams. Inside a dry box, weigh 30 g of sodium
hydroxide into a 300 mL fleaker, 70 g of sodium hydroxide into a
150 mL fleaker, and 5.0 g of ferric nitrate nonahydrate into the
sample bottle. Cap each vessel. Take the three vessels out of the
dry box. Re-weigh and record the weight of the small sample bottle
to the nearest 0.01 grams. Add 75 g of deionized water to the large
fleaker. Re-cap the large fleaker and set it in ice.
[0424] Take the cap off the large fleaker, put a TEFLON coated
stirring bar in it, weigh it and record the weight. Set the fleaker
in a large crystallizing dish on a stirring plate, add ice to the
crystallizing dish to above the level of the solution, and start
the stirring. Put a glass thermometer in the solution.
[0425] Clean and dry the delivery tip from a chlorine delivery
system. Start the chlorine addition into the sodium hydroxide
solution. Make sure the sodium hydroxide solution does not back up
into the delivery tube toward the chlorine cylinder. Watch for the
speed of bubbles and don't go too fast. Watch the temperature and
keep it below 20.degree. C. Periodically check the weight of the
fleaker plus contents and stop the chlorine addition when enough
chlorine has been added (20 g of chlorine in this example). Record
the weight of the fleaker plus contents.
[0426] Put the flask back in the ice bath with the thermometer.
Slowly begin adding the second aliquot of NaOH. Watch the
temperature closely; it is preferably around 25.degree. C. Filter
the mixture through the fritted glass filter. Put forty grams of
filtrate in a 50 mL beaker with a short stirring bar. Put the
beaker in the crystallizing dish and add water and ice or heat as
necessary to establish the temperature at the set point. Put a
thermocouple in the reaction vessel.
[0427] Begin adding ferric nitrate nonahydrate crystals from the
small sample vial and simultaneously begin recording the
temperature of the contents of the reaction vessel. It will take
four or five minutes to add the ferric crystals. Once the purple
color is strongly in evidence, begin taking samples for ferrate
(VI) analysis.
Example 12: Preparation of Ferrate(VI)
[0428] Ferrate is synthesized using the procedure of Example 1,
except 23.1 g of chlorine was used instead of 6.5 g. 40 g of coarse
glass frit filtered bleach in saturated sodium hydroxide solution
was added to a 50 mL Pyrex beaker with a TEFLON.RTM. stirring bar.
The beaker was placed in a large crystallizing dish on a magnetic
stirrer plate. The water bath maintained a temperature of
26-27.degree. C. 5 g of ferric nitrate nonahydrate was added over a
period of three minutes to begin the experiment*. During this step,
the mixture foamed up slightly causing the iron nitrate crystals to
tend to float on the foam and not mix in. At six minutes the
mixture was a dark purple color and sampling was initiated by
taking about 0.3 g and diluting to 100 g with cold buffer solution.
Six minutes coincided with the peak mixture temperature, 42.degree.
C. During the next few minutes, the foam continued to rise.
TABLE-US-00011 Actual Fraction of Reaction Time, Actual Expected
Observed Iron in Temperature, min* Wt, gm Absorbance Absorbance
(VI) State .degree. C. 6 0.31 0.97 0.14 0.14 42 8 0.33 1.03 0.25
0.24 35 10 0.31 0.97 0.24 0.25 31 16 0.31 0.97 0.27 0.28 27.5 22
0.34 1.06 0.30 0.28 31 0.32 1.00 0.29 0.29 46 0.32 1.00 0.30 0.29
*Timing began with the start of ferric nitrate nonahydrate
addition.
Example 13: Preparation of Ferrate(VI)
[0429] Ferrate is synthesized using the procedure of Example 1,
except 12 g of chlorine was used instead of 6.5 g. Reaction vessel
is a jacketed beaker maintained at 35.degree. C. Begin with 20 g of
hypochlorite/sodium. Gradually add 1.6 g of ferric nitrate
nonahydrate crystals. This is a 5 fold stoichiometric excess of
hypochlorite over ferric(III). The maximum temperature achieved
during this step was 39.degree. C.
TABLE-US-00012 Actual Actual Fraction of reaction Time, weight,
Expected Actual Iron in the temperature, min gm absorbance
absorbance (VI) state .degree. C. 15 0.3233 1.36 0.86 0.63 35.2 30
0.3427 1.44 1.14 0.79 35.2 45 0.2984 1.26 1.10 0.87 35.2 60 0.3289
1.39 1.25 0.90 35.2
Example 14: Loop Reactor Procedure
[0430] A jacketed mixing vessel set to control the temperature at
30.degree. C. is used. A reactor vessel in the form of a tube is
used with a controlled temperature setting of 35.degree. C. A
multi-head variable speed peristaltic pump set to deliver sodium
hypochlorite solution to the mixing chamber at a speed of
approximately 30 mg/sec is used. Another tube on the pump head is
used to transfer mixture from the mixing chamber to the reactor
tube.
[0431] Prepare a sample vial with more than 10 g of ferric nitrate
nonahydrate, record its weight. Prepare another sample vial with
ferric nitrate nonahydrate to deliver 3.42 g. Add 17.1 grams of
sodium hypochlorite solution to the mixing chamber. Begin the
mixing. Gradually add 3.42 g of ferric nitrate nonahydrate. Begin
timing the experiment and begin delivering sodium hypochlorite
solution from the peristaltic pump. At one minute intervals, add
0.342 grams of crystals (measured visually) into the mixing
chamber. After the 5 minute add, begin transferring reaction
mixture to the loop by positioning the inlet of the peristaltic
pump transfer tube at the surface of the reaction mixture. After
the 10, 15 and 20 minute add, record the weight of the crystal
vial. After the 20 minute add, stop delivering sodium hypochlorite
solution and stop adding crystals. Re-position the inlet to the
peristaltic pump transfer tube to near the bottom of the mixing
vessel and continue pumping from there to the Loop reactor. When
the Mixing Chamber is empty, stop the peristaltic pump. At 60
minutes, get a sample of the product from the outlet end of the
loop reactor and measure its absorbance. At 80 minutes, get a
sample of the product from the inlet end of the loop reactor and
measure its absorbance.
Example 15: Preparation of Ferrate(VI)
[0432] Ferrate is synthesized using the procedure of Example 1. 40
g of coarse glass frit filtered bleach in saturated sodium
hydroxide solution is added to a 50 mL Pyrex beaker with a
TEFLON.RTM. stirring bar. The beaker is placed in a large
crystallizing dish on a magnetic stirrer plate. The crystallizing
dish has a water/ice mixture to maintain a temperature of
19-20.degree. C. 5 g of ferric nitrate nonahydrate is added over a
period of four minutes to begin the experiment. The iron salt
distributes through the mixture but there is no visually apparent
activity for a few minutes. The temperature of the reaction mixture
does slowly elevate. Relatively suddenly, the mixture turns dark
purple. This happened 10 minutes after the start of the iron
addition, simultaneously, the reaction temperature peaked at
31.degree. C. At this point, a timer is started for the taking of
samples for Ferrate(VI) analysis. The water/ice bath maintained a
constant temperature of 19-20.degree. C.
TABLE-US-00013 Actual Fraction of Reaction Time, Actual Expected
Observed Iron in Temperature, min Wt, gm Absorbance Absorbance (VI)
State .degree. C. 2 0.30 0.95 0.37 0.39 29 6 0.39 1.24 0.66 0.53 26
10 0.31 0.98 0.55 0.56 23 15 0.32 1.02 0.64 0.63 22 25 0.30 0.95
0.64 0.67 -- 35 0.29 0.92 0.66 0.72 -- 45 0.33 1.05 0.76 0.72 -- 60
0.31 0.98 0.71 0.72 --
Example 16: Preparation of Ferrate(VI)
[0433] 40 grams of coarse glass frit filtered bleach solution is
added to a 50 mL jacketed reaction vessel with a TEFLON.RTM.
stirring bar. Controlled temperature water is circulated through
the jacket to control and establish the reaction temperature. Five
grams of ferric nitrate nonahydrate is added over a period of a few
minutes to begin the experiment.
TABLE-US-00014 Time, Actual Expected Observed Fraction of Iron
Actual Reaction min Wt, gm Absorbance Absorbance in (VI) State
Temperature, 0 C. Notes Temp control point 30.degree. C. 0 22.4
Begin iron addition 2 27 Complete iron addition 2.5 30 3.5 33.9
Beginning of reaction noted 5 0.33 1.04 0.25 0.24 31.1 10 0.32 1.01
0.40 0.40 30.7 17 0.31 0.98 0.48 0.49 30.4 25 0.33 1.04 0.59 0.57
30.4 35 0.32 1.01 0.60 0.59 30.3 45 0.34 1.08 0.695 0.64 30.5 Temp
control point 35.degree. C. 0 24 Begin iron addition 2 28.6
Complete iron addition 2.5 32 3.5 37 Beginning of reaction noted 5
0.32 0.285 1.01 0.28 36 10 0.34 0.52 1.08 0.48 35.4 17 0.34 0.61
1.08 0.56 35.3 25 0.34 0.67 1.08 0.62 35.3 35 0.31 0.68 0.98 0.69
35.3 45 0.34 0.813 1.08 0.75 35.3 60 0.43 1.11 1.36 0.82 35.2
Example 17: Preparation of Ferrate(VI)
[0434] Reaction vessel is a 30 mL beaker in a 30.degree. C. water
bath. Begin with 15 g of hypochlorite/sodium hydroxide solution.
Over two minutes, add a stoichiometric amount of ferric nitrate
nonahydrate crystals (3 g). Begin pumping bleach into the vessel at
a rate of 1.2 g per minute. Simultaneously, continuously feed iron
crystals into the vessel at a rate of 0.24 g per minute. Stop after
20 minutes, this point in time becomes time=0 in the table below.
During this period the maximum temperature was 40.degree. C. but
mostly a temperature of close to 30.degree. C. was maintained.
After the additions were stopped samples were taken for
spectrophotometric analysis.
TABLE-US-00015 Actual Actual Fraction of reaction Time, weight,
Expected Actual Iron in the temperature, min gm absorbance
absorbance (VI) state 0 C. 0 0.3267 2.93 1.121 0.38 30.1 10 0.3284
2.94 1.294 0.44 28.8 20 0.3550 3.18 1.466 0.46 28.2
Example 18: Treatment of Ballast Water with Ferrate
Objectives.
[0435] The objectives of this proposed research are to conduct a
laboratory-scale investigation of the effectiveness of ferrate to
eliminate phytoplankton, microorganisms, and zooplankton from ship
ballast water and to optimize the process with respect to
efficiency, cost, and implementation.
Work Plan.
[0436] To accomplish project objectives, the following tasks are
proposed: (1) enumerate microorganism, phytoplanktons, and
invertebrates in sea water before and after ferrate addition,
conduct tests under various contact times, dosage, and
environmental conditions (pH, salinity, and turbidity); and, (2)
pilot scale testing of ferrate treatment on sea water dockside at
the Port of Cape Canaveral; and, (3) based on results of laboratory
and dockside test findings, conduct a feasibility study for
full-scale implementation.
Preparation of Ferrate.
[0437] A bench-scale ferrate reactor, as described in U.S. patent
application Ser. No. 10/647,137, entitled "Apparatus for
synthesizing an oxidant," by Powell et al., filed Aug. 21, 2003,
which is incorporated by reference herein in its entirety, with a
capacity of 40 L is available for the synthesis of ferrate.
Sample Handling.
[0438] Five hundred ml of seawater, collected from Florida coastal
areas, is treated with ferrate under sterile conditions and stirred
for predetermined periods of time (see experimental design). Marine
organisms are enumerated prior to and following ferrate treatment.
Seawater is also filtered using 100-.mu.m filters to simulate
physical separation pretreatment and similarly treated.
Experimental Design.
[0439] The survival of marine microorganisms, phytoplankton, and
macroflora/fauna in seawater is evaluated before and after the
addition of ferrate. Untreated water acts as a control to determine
the health of the organisms in the bioassays. In all trials,
proportional data are arcsine square root transformed prior to
statistical analyses to increase normality of means and eliminate
variances that are heterogeneous between treatments. A nested ANOVA
is run to determine if the ferrate was toxic to the test organisms,
as a function of dose (5, 10, 25, 50 mg/L or higher as determined
by organism survival), contact time (5, 10, 30, and 60 minutes or
higher as determined by organism survival), turbidity (1, 5, 10
NTU, adjusted if necessary by kaolin addition), and salinity
(duplicating coastal and mid-ocean conditions). In addition, to
examine re-growth potential, treated samples are stored in the dark
for seven and 90 days at room temperature and retested for organism
survival.
Invertebrate Analysis.
[0440] For each species listed below, methods similar to those
described in Walters et al. (1996) is used. Three separate trials
are run for each test species to account for any potential genetic
or handling problems. In each trial, 20 replicate sterile,
disposable petri dishes (60.times.15 mm or larger, if needed) are
filled with 15 ml of 0.45-.mu.m filtered seawater. An additional 20
dishes contain equal amounts of filtered seawater to which various
doses of ferrate are added. Survival of organisms are enumerated
after 30 minutes, 1, 3, 6, 12, 24 and 36 hours or less if all
individuals in the treatment dishes die.
Microbiological Analysis.
[0441] Microorganism plate counts re determined using the method
described in American Public Health Association (1998).
Heterotrophic bacteria, total colifoms, and Escherichia coli are
enumerated. All glassware are washed with detergent and water,
rinsed at least two times with a 1:1 HCl solution, rinsed at least
three times with distilled water, dried and capped with aluminum
foil, and heated at 525.degree. C. for 6 hours. Samples are
collected in carbon-free bottles and transferred to sterile sample
containers, then stored at 4.degree. C. and analyze within 24
hours. For heterotrophic bacteria, samples are diluted as needed
using sterile buffered water. Using a 10-100 .mu.L pipet, 100 .mu.L
of sample is placed in the center of a NWRI agar plate, which is
then placed on the turntable. The glass spreader is dipped into
isopropyl alcohol and a flame then cooled under a hood, placed in
the middle of the sample and gently moved back and forth until the
sample is spread across the entire glass rod. After preparation the
plate is inverted and placed in a 35.degree. C. incubator for 48
hours. Samples are removed from the incubator within 48 hours of
experiment and visible colonies counted for all dilutions. Total
coliforms and E. Coli are enumerated using Colilert (IDEXX
Laboratories) a commercially available detection kit. Pseudomonas
aeruginosa and K. pneumoniae is used as standards.
Phytoplankton Analysis.
[0442] All glassware are washed with detergent and water, rinsed at
least two times with a 1:1 HCl solution, rinsed at least three
times with distilled water, dried and capped with aluminum foil,
and heated at 525.degree. C. for 6 hours. HESNW growth medium is
added to 50-ml samples of treated and untreated seawater to bring
the final volume to 200 ml. Sub-samples are obtained, preserved,
settled and viewed microscopically according to the Utermohl method
(Sutherland et al, 2001).
CONCLUSION
[0443] Thus, those of skill in the art will appreciate that the
methods, devices, and uses herein provide a relatively easy and
economical way of producing ferrate in close proximity to the site
of use.
[0444] One skilled in the art will appreciate that these methods
and devices are and may be adapted to carry out the objects and
obtain the ends and advantages mentioned, as well as those inherent
therein. The methods, procedures, and devices described herein are
presently representative of preferred embodiments and are exemplary
and are not intended as limitations on the scope of the invention.
Changes therein and other uses will occur to those skilled in the
art which are encompassed within the spirit of the invention and
are defined by the scope of the claims.
[0445] It will be apparent to one skilled in the art that varying
substitutions and modifications may be made to the invention
disclosed herein without departing from the scope and spirit of the
invention.
[0446] Those skilled in the art recognize that the aspects and
embodiments of the invention set forth herein may be practiced
separate from each other or in conjunction with each other.
Therefore, combinations of separate embodiments are within the
scope of the invention as claimed herein.
[0447] All patents and publications mentioned in the specification
are indicative of the levels of those skilled in the art to which
the invention pertains. All patents and publications are herein
incorporated by reference to the same extent as if each individual
publication was specifically and individually indicated to be
incorporated by reference.
[0448] The invention illustratively described herein suitably may
be practiced in the absence of any element or elements, limitation
or limitations which is not specifically disclosed herein. Thus,
for example, in each instance herein any of the terms "comprising",
"consisting essentially of" and "consisting of" may be replaced
with either of the other two terms. The terms and expressions which
have been employed are used as terms of description and not of
limitation, and there is no intention that in the use of such terms
and expressions indicates the exclusion of equivalents of the
features shown and described or portions thereof. It is recognized
that various modifications are possible within the scope of the
invention claimed. Thus, it should be understood that although the
present invention has been specifically disclosed by preferred
embodiments and optional features, modification and variation of
the concepts herein disclosed may be resorted to by those skilled
in the art, and that such modifications and variations are
considered to be within the scope of this invention as defined by
the appended claims.
[0449] In addition, where features or aspects of the invention are
described in terms of Markush groups, those skilled in the art will
recognize that the invention is also thereby described in terms of
any individual member or subgroup of members of the Markush group.
For example, if X is described as selected from the group
consisting of bromine, chlorine, and iodine, claims for X being
bromine and claims for X being bromine and chlorine are fully
described.
[0450] Other embodiments are within the following claims.
* * * * *